Fine-Tuning the Aperture Size of Co-ZIF-67 via Dehydration, Demethylation, and Co-Zn Hybridization

Fine-Tuning the Aperture Size of Co-ZIF-67 via Dehydration, Demethylation, and Co-Zn Hybridization | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Fine-Tuning the Aperture Size of Co-ZIF-67 via Dehydration, Demethylation, and Co-Zn Hybridization Hu Sik Kim, Ga Eon Song, Hyeonuk Choo, Woo Taik Lim This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-7579437/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 19 Nov, 2025 Read the published version in Journal of Porous Materials → Version 1 posted 12 You are reading this latest preprint version Abstract Co-ZIF-67 (Zeolitic Imidazolate Framework) is a porous material where cobalt (Co) metal ions bond with organic ligands through tetrahedral coordination. It exhibits high chemical and thermal stability similar to that of zeolite structures and is utilized for gas separation, making it an ideal target for research. A large single crystal of Co-ZIF-67 was successfully synthesized using a simple hydrothermal method. Dehydration and demethylation of the 2-methylimidazole in Co-ZIF-67, as well as altering the central metal, change the aperture size and affect the types of gases that can be separated. Therefore, in this work, dehydrated, demethylated, and hybridized Co-ZIF-67s with cobalt (Co) and zinc (Zn) were prepared in this work. These crystal structures were analyzed using single-crystal synchrotron X-ray diffraction techniques. In the untreated Co-ZIF-67 single crystal, water molecules were located at two sites opposite the 6-ring, with eight molecules per unit cell. Heat treatment at 673 K completely removed the water molecules without loss of crystallinity, and demethylation began at 683 K. As the temperature increased, the number of carbon atom at C3 per unit cell decreased, indicating the gradual removal of methyl groups. Measurement of the 6-ring aperture size revealed that heat-treated crystals had larger aperture sizes compared to untreated crystal 1. However, at 753 K, single-crystal X-ray diffraction data could not be obtained due to the loss of Co-ZIF-67 crystallinity. In the case of Co/Zn-ZIF-67 single crystals synthesized with different molar ratios, the structures were similar to those of Co-ZIF-67 single crystals, with Co exhibiting higher occupancy rates compare to Zn. Additionally, the Co/Zn-ZIF-67 demonstrated smaller unit cell parameters compared to Co-ZIF-67 (crystal 1). Consequently, the aperture size of the Co/Zn-ZIF-67 with tuning of the amount of Co and Zn was smaller than that of Co-ZIF-67 (crystal 1). ZIF-67 Demethylation Dehydration Single-crystal X-ray Diffraction Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 1. Introduction Zeolitic imidazolate frameworks (ZIFs), a unique subclass of porous metal organic frameworks (MOFs) with a sodalite-type cage similar to zeolite topology, consist of transition metal ions such as zinc and cobalt and imidazolate linkers forming 3D tetrahedral frameworks [ 1 – 10 ]. Hence, they have unique properties by combining the advantages of zeolites and MOF materials such as high surface area, high crystallinity, exceptional thermal and chemical stability, and abundant active sites [ 1 , 9 , 11 ]. These properties make ZIFs promising candidate for many applications such as gas storage and separation, medicine, catalysis, and sensor, etc. [ 1 , 7 , 10 ]. In general, ZIFs with different structures and properties can be achieved by tuning the type of metal ions and organic linker to control the shape, the size, and the pore [ 3 ]. Accordingly, over a hundred unique structures for ZIFs have been extensively studied and synthesized to date by the choice of metal ions and functionalization of the imidazolate linkers [ 1 , 3 , 10 – 16 ]. As one of ZIFs, Co-ZIF-67 consists of cobalt ions as metal nodes and 2-methylimidazolate anions as the organic linker, and forms a sodalite-type cage with a pore size of about 0.34 nm which is similar to the zeolite’s topology [ 2 , 3 , 9 ]. It is relatively easy to synthesize compared to other materials and has excellent thermal and chemical stability, high hydrophobicity, high porosity, and a large specific surface area which are favorable for the adsorption reactions due to its strong affinity for guest molecules [ 2 ]. Accordingly, Co-ZIF-67 has been shown to have excellent activity for many guest molecules in various applications as gas storage and separation including volatile organic compounds adsorption and separation [ 1 , 5 , 9 , 10 ]. In general, the gas adsorption properties of the Co-ZIF-67 are strongly influenced by the distribution of water molecules and demethylation of the 2-methylimidazolate ligands in the framework of ZIFs because the size of the pores changes and the type of gas that can be separated changes, when the water molecules are removed and demethylation occurs by thermal treatment [ 6 ]. Furthermore, Co-ZIF-67 is very sensitive to moisture and is unstable in an aqueous solution or water [ 10 , 12 ]. According to previous reports, although Co-ZIF-67 has exhibited high adsorption ability for various gases, its adsorption ability significantly decreases when exposed to moisture under ambient conditions. Moreover, adsorption ability is drastically reduced after immersion in water due to the collapse of the crystal structure [ 10 , 12 ]. Therefore, the water sensitivity and demethylation of Co-ZIF-67 are key parameters for its application in commercial settings. However, to the best of our knowledge, despite previous efforts in studies on the adsorption applications of Co-ZIF-67, detailed information about the chemical and thermal stability in the presence moisture at ambient conditions is still not fully understood or very limited. Here, for development of gas separation, we investigate the behavior of water molecules in the framework of Co-ZIF-67 by increasing heating temperature under vacuum more precisely and also show the framework structure of demethylation on the 2-methylimidazolate ligands in Co-ZIF-67 at specific temperatures. Finally, we want to observe the change in the aperture size of the 6-ring when complete dehydration and demethylation occurs. In general, most ZIF structures studied are based on single metals, and their properties (surface area, aperture sizes, porosity, thermal stability and so on) primarily depend on the metal species [ 10 ]. In particular, the gas diffusion properties of isostructural ZIFs with different metal centers depend on both their crystallographically-defined aperture sizes with different metal and the stiffness of the corresponding metal-nitrogen [ 16 ]. Accordingly, by precisely controlling the metal substitution in Co-ZIF-67, one can potentially fine-tune its effective aperture sizes, which has significant implications for gas separation applications. According to the previous reports, the dual metallic Zn/Co-ZIF by tuning the amount of Co and Zn has different physical properties (surface area, aperture sizes, porosity, thermal stability, and so on) and chemical properties (CO 2 -TPD, NH 3 -TPD) compared with single metal ZIFs [ 10 ]. Therefore, the construction of mixed metal-ZIF would be a fascinating option that provides an effective way to tune or introduce new properties in ZIFs [ 10 , 16 ]. For this reason, mixed metal-ZIFs have been extensively studied and synthesized in recent years, but the direct synthesis and characterization of mixed metal-ZIFs seem to be still challenging [ 10 , 16 ]. Herein, we synthesize single crystals of Co/Zn Hybrid ZIF-67 (hereafter, Co/Zn-ZIF-67) and investigate the property changes of Co-ZIF-67 through crystal structure analysis. This detailed information could provide new insights into the practical application of Co/Zn-ZIF-67 in gas adsorption, gas separation, and catalysis. In the present work, the large single crystal of Co-ZIF-67 was successfully synthesized through the facile hydrothermal method and fully characterized by systematic physical and chemical measurements such as single-crystal synchrotron X-ray diffraction technique, scanning electron microscope, and thermal gravimetric and differential thermal analysis. Based on these results, the properties of the Co-ZIF-67 were also compared with those of Zn-ZIF-8. In addition, large single crystals of Co/Zn-ZIF-67 with various Co/Zn ratios were synthesized, showing that Zn substitution can potentially tune the aperture size of ZIF-67. 2. Experimental Section 2.1. Synthesis of Large Single Crystal of Co-ZIF-67 The chemicals used for synthesizing included cobalt nitrate hexahydrate (Co(NO 3 ) 2 ·6H 2 O, Alfa Acesar), 2-methylimidazole (C 4 H 6 N 2 , Sigma Aldrich), methanol (CH 4 O, Sigma Aldrich), dimethylformamide (C 3 H 7 NO, Jun Sei), and nitric acid (HNO 3 , Sam Jung). All the chemical reagents were used without further purification. Large single crystal of ZIF-67 was prepared by following the recopied by Kwon et al . with a slight modification [ 17 ]. In a typical synthesis, 1.05 g of cobalt nitrate hexahydrate and 0.27 g 2-methylimidazole were dissolved in 108 mL of dimethylformamide containing six drops of 1 M nitric acid and stirred vigorous for 10 min. Above solution was transferred into a 250 mL glass bottle kept in an oven at 403 K for 144 h. After the reaction, the glass bottle was naturally cooled down to room temperature and the product was washed with methanol by sonication several times. Then, it was dried at 323 K for 12 h. 2.2. Dehydration, Demethylation, and Decomposition Each of 10 Co-ZIF-67 single crystals was lodged in a Pyrex capillary. Crystal 1 was as-synthesized without any thermal treatment and the capillary containing the crystal was sealed with a torch to block from the outside air. Crystals 2 to 8 were attached to a vacuum system, and the crystals were thermal treated at 673, 683, 688, 693, 698, 703, and 723 K, respectively, under dynamic vacuum for 48 h (see Table S1 ). Crystals 9 and 10 were thermally treated ZIF-67 at 683 K under dynamic vacuum for 48 and 54 h, respectively (see Table S1 ). The crystal in each capillary was sealed off under vacuum from the line. 2.3. Synthesis of Large Single Crystal of Co/Zn-ZIF-67 Mixed-metal Co/Zn-ZIF-67 single crystals were synthesized based on the Co-ZIF-67 synthesis protocol described above, with slight modifications using the molar ratio of Co to Zn in the synthesis solution (Co(NO 3 ) 2 ·6H 2 O : Zn((NO 3 ) 2 ·6H 2 O) at 1:3, 1:1, and 3:1, respectively, in the presence of the ligand solution (2-methylimidazole). After mixing the metal precusors, including both cobalt salt and zinc salt, with the ligand solution, the mixture was transferred into a 250 mL glass bottle and heated in an oven at 403 K for 144 h. After the reaction, the glass bottle was naturally cooled down to room temperature and the product was washed with methanol by sonication several times. Then, it was dried at 323 K for 12 h. 2.4. Characterization The morphology, size, and purity of the synthesized Co-ZIF-67 and Co/Zn-ZIF-67 single-crystals were characterized using scanning electron microscope (SEM, Tescan VEGA II LMU). Scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis was done to determine the compositions of Co/Zn-ZIF-67. A comparison of the compositions as determined by crystallographic data and SEM-EDX analysis is presented in Table 1 . Thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) measurements were performed by thermal analyzer (TG-DTA, Rigaku TG-DTA 8122). For this purpose, ca. 10 mg samples were filled into an alumina crucible and heated in a continuous-flow of nitrogen gas with a ramp rate of 10 ℃/min from 313 to 773 K. Table 1 Crystal composition (at %) by crystallographic (SXRD) and SEM-EDX analyses for crystals 11, 12, and 13 Element a Crystal 11 Crystal 12 Crystal 13 SXRD SEM-EDX b SXRD SEM-EDX b SXRD SEM-EDX b Co 5.32 5.11 4.81 4.56 6.03 5.96 Zn 2.37 2.33 2.88 3.24 1.67 1.55 N 30.77 29.25 30.77 29.09 30.77 29.46 C 61.54 63.31 61.54 63.11 61.54 63.03 a Only Co, Zn, N, and C were found in these crystals. b The ZIF crystal can be expected to have suffered some decomposition upon exposure to the atmosphere and the action of the electron beam. This can be a significant source of error. 2.5. X-ray Diffraction. Diffraction data were collected for the thirteen crystals using synchrotron X-radiation. Temperature was maintained at 100(1) K by a flow of cold nitrogen gas. Preliminary cell constants and an orientation matrix were determined from 72 sets of frames collected at scan intervals of 5 o with an exposure time of 1 s per frame. The basic scale file was prepared using the HKL3000 program [ 18 ]. The reflections were successfully indexed by the automated indexing routine of the DENZO program [ 18 ]. The diffraction data were harvested by collecting 72 sets of frames with 5 o scans with an exposure time of 1 s per frame. These highly redundant data sets were corrected for Lorentz and polarization effects, and a very small correction for crystal decay was applied. The space group I \(\:\stackrel{-}{4}\) 3 m , standard for ZIF-67, was determined by the program XPREP [ 19 ]. A summary of the experimental and crystallographic data with some additional details is presented in Table S1 . 3. Structure Determination Full-matrix least-squares refinement (SHELXL2014) was done on F 2 using all data for each crystal [ 20 ]. Each initial refinement used anisotropic thermal parameters and converged to the high error indices. Fixed weights were used initially; the final weights were assigned using the formula w = 1/[σ 2 ( F o 2 ) + ( aP ) 2 + bP ] where P = [Max( F o 2 ,0) + 2 F c 2 ]/3; the refined values of a and b are given in Table S1 . Neutral atomic scattering factors within SHELX-2014 were used, and all were modified to account for anomalous dispersion [ 21 , 22 ]. All non-hydrogen atoms were refined using anisotropic thermal parameters. Hydrogen atoms were included in the structure factor calculation at idealized positions by using riding model. The final error indices are given in Table S1 . The structural parameters are given in Table S2 and selected interatomic distances and angles can be found in Table S3. 4. Results 4.1. Morphology characteristic of Co-ZIF-67 We have first used optical microscope (OM) for confirming the synthesis of large single crystal Co-ZIF-67 and Co/Zn-ZIF-67. Similar to the previously reported Co-ZIF-67, we found that the product was pure-phase ZIF-67 materials with polyhedral shape and purple color (see Fig. 1 (a)). The Co-ZIF-67 is a deep purple in color whereas Co/Zn-ZIF-67 is light purple. The SEM images of Co-ZIF-67 were shown in Figs. 1 (b) and (c). It could be seen that all Co-ZIF-67 crystals have a large quantity of regular particles with uniform and well-defined dodecahedron with sharp edges and smooth faces as reported in previous studies [ 2 , 7 , 9 , 15 , 16 ]. In addition, as shown in the SEM images, the crystal sizes of Co/Zn-ZIF-67 (100–200 ㎛) are decreased compared to those of Co-ZIF-67 (100–300 ㎛). The presence of Co and Zn in Co/Zn-ZIF-67 single crystal were investigated by single-crystal X-ray diffraction techniques and SEM-EDX analysis, respectively (see Table 1 , 2 , and Fig. 1 (c)). The SEM-EDX analysis revealed that the Co content is higher than the Zn content in all Co/Zn-ZIF-67 single crystal which was in good agreement with the result of a crystallographic study (see Tables 1 and 2 ). Table 2 Positional, Thermal, and Occupancy Parameters a of Crystals 1 to 13 atom Wyckoff position x y z U 11 b or U iso U 22 U 33 U 23 U 13 U 12 Occupancy c crystal 1 (in situ Co-ZIF-67) Co1 12( d ) 0 5000 7500 655(3) 655(3) 638(3) 0 0 0 12 N1 48( h ) 898(1) 5332(1) 8176(1) 687(10) 661(9) 684(10) 18(8) -30(8) -23(8) 48 C1 24( g ) 1233(1) 4935(3) 8767(1) 675(8) 635(17) 675(8) 8(10) 6(10) -8(10) 24 C2 48( h ) 1864(2) 6041(2) 8698(2) 790(14) 675(12) 821(15) 72(10) -91(12) -90(10) 48 C3 24( g ) 955(2) 4144(2) 9045(2) 808(13) 713(17) 808(13) 82(12) -10(16) -88(12) 24 O1 8( c ) 1866(17) 8134(17) 8134(17) 2199(193) 2199(193) 2199(193) 531(173) -531(173) -531(173) 5.0(5) O2 8( c ) 3194(36) 6806(36) 6806(36) 3083(783) 3083(783) 3083(783) -86(534) 86(534) 86(534) 2.9(7) H2 d 48( h ) 2218 6446 8798 913 H3a d 24( g) 1395 3791 9074 1164 H3b d 24( g ) 573 3941 8681 1164 H3c d 24( g ) 720 4195 9557 1164 crystal 2 (fully dehydrated at 673 K) Co1 12( d ) 0 5000 7500 612(4) 612(4) 594(5) 0 0 0 12 N1 48( h ) 901(2) 5322(2) 8171(2) 668(18) 593(15) 651(17) 21(13) -59(15) -60(14) 48 C1 24( g ) 1228(2) 4939(6) 8772(2) 676(16) 614(32) 676(16) 27(23) 26(20) -27(23) 24 C2 48( h ) 1873(3) 6022(3) 8684(3) 751(26) 644(21) 788(25) 45(19) -66(19) -76(19) 48 C3 24( g ) 940(3) 4150(4) 9060(3) 759(21) 726(35) 759(21) 75(22) -111(31) -75(22) 24 H2 d 48( h ) 2231 6426 8776 873 H3a d 24( g) 1258 3981 9796 1122 H3b d 24( g ) 401 4200 9226 1122 H3c d 24( g ) 978 3772 8642 1122 crystal 3 (dehydrated at 683 K) e C3 24( g ) 937(5) 4147(6) 9067(5) 1055(64) 866(97) 1055(64) 137(49) -107(72) -137(49) 23.6(5) crystal 4 (dehydrated at 688 K) e C3 24( g ) 927(5) 4150(8) 9073(5) 1301(77) 1175(135) 1301(77) 205(74) -309(84) 1205(74) 23.4(6) crystal 5 (dehydrated at 693 K) e C3 24( g ) 927(5) 4150(8) 9073(5) 1301(77) 1175(135) 1301(77) 205(74) -309(84) 1205(74) 23.0(6) crystal 6 (dehydrated at 698 K e C3 24( g ) 934(7) 4162(12) 9066(7) 1423(107) 1363(217) 1422(107) 137(103) -241(112) -137(103) 22.6(4) crystal 7 (dehydrated at 703 K) e C3 24( g ) 927(5) 4150(8) 9073(5) 1301(77) 1175(135) 1301(77) 205(74) -309(84) 1205(74) 22.9(3) crystal 8 (dehydrated at 723 K) e C3 24( g ) 927(5) 4150(8) 9073(5) 1301(77) 1175(135) 1301(77) 205(74) -309(84) 1205(74) 23.1(8) crystal 9 (dehydrated at 683 K for 54 h) Co1 12( d ) 0 5000 7500 1032(12) 1039(11) 977(15) 0 0 0 12 N1 48( h ) 900(4) 5317(5) 8168(4) 991(58) 1073(70) 1064(53) 112(48) -129(41) -112(43) 48 C1 24( g ) 1235(5) 4932(13) 8765(5) 1019(54) 833(101) 1019(54) -47(76) 35(83) 47(76) 24 C2 48( h ) 1313(4) 6011(5) 8128(4) 1303(72) 1035(68) 1302(77) 202(54) -195(58) -204(57) 48 C3 24( g ) 930(6) 4151(9) 9070(6) 1253(85) 1064(148) 1253(85) 181(74) -320(93) -181(74) 22.3(4) H2 d 48( h ) 1219 6418 7768 1456 H3a d 24( g) 399 4218 9265 1785 H3b d 24( g ) 1265 3969 9492 1785 H3c d 24( g ) 931 3770 8649 1785 crystal 10 (dehydrated at 683 K for 60 h) e C3 24( g ) 934(5) 4147(6) 9066(5) 1152(63) 916(87) 1152(63) 172(49) -200(73) -172(49) 19.3(11) crystal 11 (Co/Zn-ZIF-67, no dehydrated) Co1 12( d ) 71(5) 4935(6) 7558(6) 389(25) 8.3(2) Zn1 12( d ) 0 5000 7500 284(123) 284(123) 329(115) 0 0 0 3.7(2) N1 48( h ) 893(2) 5345(2) 8177(2) 543(11) 549(11) 566(12) 18(9) -44(9) -22(9) 48 C1 24( g ) 1236(1) 4934(4) 8764(1) 545(9) 480(22) 545(9) 2(12) 22(11) -2(12) 24 C2 48( h ) 1845(2) 6063(2) 8714(2) 715(18) 545(13) 682(17) 63(12) -88(14) -123(12) 48 C3 24( g ) 972(2) 4135(3) 9028(2) 705(15) 554(19) 705(15) 79(13) -137(19) -79(13) 24 O1 8(c) 1923(12) 8077(12) 8077(12) 1363(92) 3.9(1) O2 8(c) 3209(22) 6791(22) 6791(22) 2823(346) 4.1(1) H2 d 48( h ) 2191 6477 8821 777 H3a d 24( g) 1303 3957 9453 981 H3b d 24( g ) 434 4163 9207 981 H3c d 24( g ) 1008 3771 8595 981 crystal 12 (Co/Zn-ZIF-67, no dehydrated) f Co1 12( d ) 84 4926(6) 7574(6) 363(36) 7.5(1) Zn1 12( d ) 0 5000 7500 470(90) 470(90) 494(87) 0 0 0 4.5(1) O1 8(c) 1901(10) 8099(10) 8099(10) 1699(91) 6.1(1) O2 8(c) 3335(38) 6665(38) 6665(38) 3038(373) 1.9(1) crystal 13 (Co/Zn-ZIF-67, no dehydrated) f Co1 12( d ) 74(6) 4939(7) 7564(8) 488(22) 9.4(1) Zn1 12( d ) 0 5000 7500 346(135) 346(135) 330(198) 0 0 0 2.6(1) O1 8(c) 1936(13) 8064(13) 8064(13) 1149(92) 4.9(1) O2 8(c) 3161(32) 6839(32) 6839(32) 1785(332) 3.1(1) a Positional and thermal parameters × 10 4 are given. Numbers in parentheses are the esds in the units of the least significant figure given for the corresponding parameter. b The anisotropic temperature factor is exp[-2π 2 a −2 ( U 11 h 2 + U 22 k 2 + U 33 l 2 + 2 U 23 kl + 2 U 13 hl + 2 U 12 hk )]. c The Occupancy factor is given as the number of atoms. d Hydrogen atom positions were calculated by the suite of computer programs SHELXL-2017. e The framework atoms (Co,N, C(C1 and C2), and H) were omitted to avoid the repetition of similar data. f The framework atoms (N, C, and H) were omitted to avoid the repetition of similar data. 4.2. Thermal stability of ZIF-67 The thermal stability of Co-ZIF-67 crystals was evaluated by TG-DTA analysis under an N 2 atmosphere. The result of TG-DTA of Co-ZIF-67 crystal with increasing temperature was shown in Fig. 2 . Similar to the previously reported Co-ZIF-67, the TGA curve shows a slight initial weight loss of 3.2% for Co-ZIF-67 between 300 and 523 K, which is attributed to the removal of guest molecules and unreacted species [ 7 , 14 , 15 ]. Subsequently, a significant weight loss of Co-ZIF-67 was observed in the temperature range of 523 ~ 773 K due to the decomposition of organic ligands and the collapse of the framework corresponding to the exothermic peak in the DTA curve, which is a good agreement with the several previous TGA studies on Co-ZIF-67 [ 7 , 10 , 14 , 15 ]. 5. Description of the Structures 5.1. Framework of Co-ZIF-67 Co-ZIF-67 has eight single 6-rings and four single 4-rings like sodalite zeolite (see Fig. 3 ). The average distance Co, the central metal, and N of imidazolate, the organic ligand, was 1.99 Å, which was observed similar to the known distance (see Table S3). The N1–Co–N1 bond angle is almost 109.5°, nearly perfectly tetrahedral (see Table S3). The average distances between the atoms in the organic ligands forming the structure were 1.34, 1.36, and 1.51 Å for N1–C1, N1–C2, and C1–C3, respectively (see Table S3). These are similar to those of the single-crystal structure of 2-methylimidazole [ 23 ]. 5.2. Structure of Crystal 1. In the structure of crystal 1, 8 water molecules per unit cell were found in two crystallographic sites (see Table 2 , S2, Fig. 3 , and 4 ). The 5.0(5) water molecules per unit cell at O1 were located opposite 6-rings in the cavity of Co-ZIF-67 (see Fig. 4 (a)). Each water molecule at O1 is recessed ca . 1.827 Å into the cavity from their plan. The remaining 2.9(7) water molecules per unit cell at O2 were located opposite 6-rings outside the cavity of Co-ZIF-67 (see Fig. 4 (b)). Each water molecule at O2 extends out of the cavity ca . 1.999 Å from its Co plane (see Table S3). The water molecules at O1 and O2 were interacting with the hydrogens of the C-C bonds of three ligands on the 6-ring plane (see Fig. 4 ). These distances between the water molecules at O1 and O2 and the hydrogen of ligand, O1–H2 and O2–H2, were 3.119 and 3.786 Å, respectively (see Table S3). In this structure, water molecules were fully occupied at 6-ring planes (see Figs. 3 and 4 ). 5.2. Structure of Crystal 2. Crystal 2 was thermally treated Co-ZIF-67 at 673 K under a dynamic vacuum of 6.5 × 10 − 6 Pa for 48 h. In this structure, no water molecules were found (see Table 2 , S2, and Fig. 5 ). The 8 water molecules per unit cell at O1 and O2 in the structure of crystal 1 were completely removed when treated at 673 K under a dynamic vacuum of 6.5 × 10 − 6 Pa. Despite complete dehydration, this structure retained its crystallinity without any signs of crystal decomposition. 5.3. Structures of Crystal 3–8. Crystals 3–8 were thermally treated at 683, 688, 693, 698, 703, and 723 K, respectively, under a dynamic vacuum for 48 h. There were no water molecules in the structures of crystals 3–8 as in the structure of crystal 2. However, the occupancy of methyl group at C3 of the 2-methylimidazolate ligands per unit cell in Co-ZIF-67 was decreased slightly as the heating temperature increased (see Table 2 , Table S2 and Fig. 6 (a)). The occupancy of methyl group at C3 of the ligands per unit cell in the structure of crystals 3–8 were 23.6(5), 23.4(6), 23.0(6), 22.6(4), 22.9(3), and 23.1(8), respectively (see Table 2 and Table S2). It is noted that, no single-crystal X-ray diffraction data were obtained at 753 K due to the loss of crystallinity of Co-ZIF-67. 5.4. Structure of Crystals 9 and 10. The crystal 9 and 10 were thermally treated with heating times of 54 and 60 h, respectively, at 683 K under a dynamic vacuum of 6.2 × 10 − 6 Pa. In these structures, as in crystals 3 to 8, no water molecules were present. The occupancy of methyl group at C3 of the 2-methylimidazolate ligands per unit cell in ZIF-67 was decreased as the heating time increased (see Fig. 6 (b)). The occupancies of methyl group at C3 of the ligands per unit cell in the structure of crystal 9 and 10 were 22.3(4) and 19.3(11), respectively (see Table 2 and S2). 5.5. Structures of Crystal 11–13. The crystals 11, 12, and 13 were synthesized with Co/Zn molar ratios of 1:3, 1:1, and 3:1, respectively, in the synthesis solution. The Co/Zn-ZIF-67 has a tetrahedral structure because each metal center coordinates with four nitrogen atoms of four discrete ligands (see Fig. 7 ). This is similar as in the crystal structure of Co-ZIF-67. However, it is important to note that in the bimetallic M-ZIF framework, M can represent either Zn or Co, and its position within the crystal structure is completely random. Furthermore, the Co/Zn ratio in the ZIF framework is significantly influenced by the Co/Zn ratio employed during synthesis. The occupancies of Co and Zn per unit cell were 8.3 and 3.7 in crystal 11, 7.5 and 4.5 in crystal 12, and 9.4 and 2.6 in crystal 13, respectively (see Table 2 and Table S2). The Co contents are higher than the Zn contents in all three crystals. This preferential inclusion of Co ions is possibly attributed to the use of the Co-ZIF-67 synthesis method. The average distances between Co, the central metal, and the N of imidazolate were 1.9852, 1.9864, and 2.0101 Å for crystal 11, 12, and 13, respectively, whereas the average distances between Zn and N were 1.9830, 1.9834, and 1.9779 Å in crystal 11, 12, and 13, respectively (see Table S3). In all three crystals, water molecules at O1 and O2 were located opposite 6-rings in the cavity of Co/Zn-ZIF-67. The occupancies of water molecules at O1 and O2 per unit cell were 3.9 and 4.1 in crystal 11, 6.1 and 1.9 in crystal 12, and 4.9 and 3.1 in crystal 13, respectively (see Table 2 and Table S2). The water molecules at O1 and O2 were interacting with the hydrogen atom bonded to six carbon atoms of the ligand at C2 on the 6-ring plane. The positions and bonding distances of water molecules to framework are similar to those in crystal 1. 6. Discussion 6.1. Water Molecules in Co-ZIF-67 The behavior of water molecules in the structures of Co-ZIF-67 treated at different temperatures under a dynamic vacuum can be seen from the crystallographic results of crystal 1 and 2. The water molecules in the structure of Co-ZIF-67 are ca. 8 per unit cell at the near center of the 6-ring planes as seen in the crystal 1 without any treatment. The water molecules in the structure of Co-ZIF-67 are likely to come from the reagent such as Cobalt nitrate hexahydrate (Co(NO 3 ) 2 ·6H 2 O) used in its synthesis. The water molecules were completely removed at 673 K without the loss of crystallinity as seen in the structure of crystal 2. The unit cell constants were not significantly changed by complete dehydration in the framework of Co-ZIF-67 (see Table S1 ). As a result of measuring the aperture size of the 6-ring, it was found that the aperture size of 5.824 Å in crystal 2 was smaller than that in crystal 1 (5.840 Å) due to the removal of water molecules from the 6-ring (see Table S4). 6.2. Demethylation of ZIF-67. Generally, the demethylation should occur first before the breaking of Co-N coordination bond and C–C bonds of the imidazolate ligand, because the C–C bond between the imidazolate ring and the methyl group is relatively weak compared with the Co–N coordination bond and the other bonds of the imidazolate ligand [ 6 ]. In this work, when heated at 673 K for 48 h (crystal 2) under a dynamic vacuum of 6.5 × 10 − 6 Pa, Co-ZIF-67 crystal showed no demethylation of the 2-methylimidazolate ligands despite complete dehydration. However, when thermally treated at 683 K for 48 h (crystal 3) under a dynamic vacuum of 6.5 × 10 − 6 Pa, the occupancy of carbon of the methyl group at C3 of the 2-methylimidazolate ligands began to decrease in this crystal, indicating demethylation. As the heating temperature increased from 683 to 723 K, the number of carbons of the methyl group at C3 of the 2-methylimidazolate ligands in Co-ZIF-67 decreased slightly (see Table 2 , Table S2, and Fig. 6 ). The reduction percentages of the methyl group at C3 were 2%, 3%, 4%, 6%, 5%, and 4% at heating temperatures of 683, 688, 693, 698, 703, and 723 K under a dynamic vacuum, respectively. Additionally, the occupancy of the methyl group at C3 of the 2-methylimidazolate ligands was significantly decreased at 683 K with increasing heating time with 2%, 7%, and 20% for 48, 54, and 60 h, respectively. As a result of measuring the aperture size of the 6-ring, the aperture size in the heat-treated crystals tended to be larger than that in the untreated crystals (see Fig. 8 ). This result indicates that the systematic reduction of the methyl group, depending on the heating temperature and time under a dynamic vacuum, led to an increase in the aperture size of the structures, which can alter the type of gas separated during gas separation. When a single crystal of Co-ZIF-67 was dehydrated at 753 K under a dynamic vacuum, no single-crystal X-ray diffraction data were obtained due to the loss of Co-ZIF-67 crystallinity. This result shows that the decomposition of ligands in Co-ZIF-67 is complete, which is consistent with previous TGA studies indicating that Co-ZIF-67 has thermal stability up to 673 K and is completely decomposed at temperatures higher than 723 K [ 7 , 10 , 15 ]. The observation suggests that the remarkable thermal stability of Co-ZIF-67 allows it to be used in a variety of applications where relatively high temperatures are required. 6.3. Structural Comparison with Zn-ZIF-8 and Co-ZIF-67. Zn-ZIF-8 and Co-ZIF-67 are formed by bridging 2-methylimidazolate with Zinc and Cobalt, respectively [ 10 ]. They are iso-structural ( i.e ., crystallographically same structure) with different metal nodes and have same crystallographic features such as crystal system and space group with similar lattice parameters. However, according to the previous studies, despite similar formation mechanisms, they have some different physical properties and chemical properties due to the difference in metal ions present in the imidazolate linker [ 9 , 10 ]. In our previous crystallographic work, we have extensively studied the behavior of water molecules, demethylation, and decomposition of Zn-ZIF-8 upon thermal treatment [ 6 ]. When the Zn-ZIF-8 [ 6 ] and Co-ZIF-67 (in this work) are compared, it can be seen that there are some differences in the distribution of water molecules and the thermal stability with increasing temperature. When the ZIFs are exposed to water, water molecules are located at three crystallographic sites on opposite 4-ring, near center of 6-ring plane, and between two 6-rings [ 6 ]. Water molecule energetically preferred and the first to be filled in the 6-ring site, the remaining water molecules move to other sites under the increasing number of water molecules [ 6 ]. These Water molecules are interacting with the hydrogen of the methyl group of the 2-methylimidazolate ligands [ 6 ]. In the structure of Zn-ZIF-8, water molecules occupy two crystallographic sites at opposite 4-ring and near center of 6-ring plane. However, in the structure of Co-ZIF-67, water molecules are located only one crystallographic site at near center of 6-ring plane. Unlike the structure of Zn-ZIF-8, no water molecules are found at opposite 4-ring, due to the relatively low content of water molecules in the structure of Co-ZIF-67. When heated at 673 K for 48 h under a dynamic vacuum, the Co-ZIF-67 crystal showed complete dehydration but water molecules are not completely removed in the Zn-ZIF-8 crystal under the same condition, which is completely dehydrated at 723 K. In addition, the demethylation occurs first at 683 K under a dynamic vacuum in the Co-ZIF-67 crystal, whereas it occurs at 773 K under a dynamic vacuum in the Zn-ZIF-8 crystal. With increasing the heating temperature, the occupancy of the methyl group at C3 of the 2-methylimidazolate ligand is decreased in the both ZIF crystals. Subsequently, the thermal decomposition in the structure of the Co-ZIF-67 is observed at 753 K under a dynamic vacuum. On the other hand, unlike the structure of the Co-ZIF-67, the thermal decomposition in the structure of Zn-ZIF-8 is exhibited at 798 K under a dynamic vacuum. This result indicates that the thermal stability of the Co-ZIF-67 crystal is slightly lower than that of the Zn-ZIF-8 crystal as seen in previous work [ 10 ]. It is strongly related to the coordination capability of Co ion to 2-methylimidazolate, which is weaker than that of Zn ion [ 10 ]. 6.4. Hybridization of Central Metal in ZIF-67 In this work, three types of Co/Zn-ZIF-67 single crystal with various Co/Zn ratios were synthesized to demonstrate the possibility of tuning the aperture size of Co-ZIF-67 by incorporating Zn centers. The structure and oxygen ion pattern of these crystals are shown to be similar to that of Co-ZIF-67 (crystal 1). However, the unit cell constants were significantly changed by incorporating Zn centers in the framework of Co-ZIF-67 (see Table S1 ). Co/Zn-ZIF-67s (crystal 11, 12, and 13) have smaller unit cell parameters as compared to Co-ZIF-67 (crystal 1), which could be an effect of the smaller Zn–N distance of the material. The distance of metal and N distance is an important factor for determining the crystallographically-defined aperture size [ 16 ]. Finally, as a result of measuring the aperture size of the 6-ring, the aperture sizes of the Co/Zn-ZIF-67s (5.795, 5.787, and 5.768 Å for crystal 11, 12, and 13, respectively) were smaller than that of the ZIF-67 (5.824 Å for crystal 1) (see Table S4 and Fig. 8 ). These findings indicate that the Co/Zn-ZIF-67 can tune the aperture size of the Co-ZIF-67 material for gas selectivity while maintaining the crystal structure of Co-ZIF-67 (see Fig. 8 ). 7. Summary The rhombic dodecahedral large single crystals of Co-ZIF-67 was successfully synthesized through the facile hydrothermal method and its structure was determined by single-crystal X-ray diffraction techniques. In the structure of Co-ZIF-67, about 8 water molecules were located only one crystallographic site at near center of 6-ring plane, these water molecules at O1 and O2 were completely removed at 673 K for 48 h under a dynamic vacuum. The demethylation was the first to occur at 683 K under a dynamic vacuum in Co-ZIF-67 crystal. With increasing heating temperature, the occupancy of the methyl group at C3 of the 2-methylimidazolate ligand was decreased with 2%, 3%, 4%, 6%, 5%, and 4% at 683, 688, 693, 698, 703, and 723 K, respectively. As a result of measuring the aperture size of the 6-ring, the aperture size in the heat-treated crystals tended to be larger than that in the untreated crystals. Single-crystal X-ray diffraction data could not be obtained at 753 K under a dynamic vacuum due to the loss of Co-ZIF-67 crystallinity. Additionally, single crystals of Co/Zn-ZIF-67 containing both Co and Zn center were successfully synthesized; their crystal structure closely resembles that of Co-ZIF-67. The percentages of Co and Zn in ZIF-67 depend on the Co/Zn ratio used during synthesis, and the Co content exceeds that of Zn in all three crystals. By incorporating Zn centers into the framework of Co-ZIF-67, the unit cell parameter and the aperture size of the Co/Zn-ZIF-67 are smaller than those of Co-ZIF-67. Consequently, dehydration, demethylation, and central-metal hybridization of Co-ZIF-67 with Zn offer promising approaches to fine-tuning its aperture sizes for gas adsorption and separation applications. Declarations Author Contribution HSK , GES, and WTL wrote the main manuscript text and HC prepared figures 1-3. All authors reviewed the manuscript. Acknowledgements This research was supported by the Gyeongsangbuk-do RISE(Regional Innovation System & Education) project. The authors wish to thank the staff at Beamline 2D SMC at the Pohang Light Source, Korea, for assistance during data collection. References C. Duan, Y. Yu, H. Hu, Green. Energy Environ. 7 , 3 (2022) X. Feng, M. Carreon, J. Cryst. Growth. 418 , 158 (2015) W. Hu, B. Pattengale, J. Huang, J. Chem. Phys. 154 , 240901 (2021) G. Zhong, D. Liu, J. Zhang, J. Mater. Chem. A 6 , 1887 (2018) S. Ahmed, D. Bagchi, H. Katouah, M.N. Masan, H. Altass, S.K. Pal, Sci. Rep. 9 , 19372 (2019) D.J. Moon, J.M. Lee, M.R. Bae, H. Jeong, W.T. Lim, J. Phys. Chem. C 123 , 31032 (2019) J. Qian, F. Sun, L. Qin, Mater. Lett. 82 , 220 (2012) W. Meng, Y. Wen, L. Dai, Z. He, L. Wang, Sens. Actuators B 206 , 852 (2018) J. Qin, S. Wang, X. Wang, Appl. 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Chruszcz, HKL-3000, the integration of data reduction and structure solution from diffraction images to an initial model in minutes. Acta Crystallogr. Sect. D: Struct. Biol. D62 , 859 (2006) Bruker, -AXS (ver. 6.12), XPREP , Program for the Automatic Space Group Determination. Bruker AXS Inc., Madison, (2001) G.M. Sheldrick, A short history of SHELXL . Acta Crystallogr. Sect. A: Found. Adv. A64 , 112 (2008) D.T. Cromer, Acta Crystallogr. 18 , 17 (1965) J.A. Ibers, W.C. Hamilton (eds.), International Tables for X-ray Crystallography , vol. IV (Kynoch, Birmingham, England, 1974), pp. 148–150 B. Hachuła, M. Nowak, J. Kusz, J. Chem. Crystallogr. 40 , 201 (2010) Additional Declarations No competing interests reported. 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07:18:38","extension":"xml","order_by":20,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":138121,"visible":true,"origin":"","legend":"","description":"","filename":"1011b2865c7a435da4f466b50d82edd91structuring.xml","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/aae5a5ebd856139f37cbe22c.xml"},{"id":91956002,"identity":"7e220877-edcf-4d58-9a8c-860cbb1c5dda","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"html","order_by":21,"title":"","display":"","copyAsset":false,"role":"acdc-reference","size":150298,"visible":true,"origin":"","legend":"","description":"","filename":"earlyproof.html","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/36457f77c89b1cfef975f8e6.html"},{"id":91956772,"identity":"df0285e7-1747-446f-9452-d5c2e6bb5a25","added_by":"auto","created_at":"2025-09-23 07:18:38","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":924177,"visible":true,"origin":"","legend":"\u003cp\u003e(a) OM image of Co-ZIF-67 crystals (b) SEM images of Co-ZIF-67 crystals (c) SEM-EDX spectrum of Co/Zn-ZIF-67 crystal\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/7e7cc1a7e47e87516c66406c.png"},{"id":91955972,"identity":"0ca5c414-a1d7-4780-8762-f63355285005","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"jpg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":58223,"visible":true,"origin":"","legend":"\u003cp\u003eTGA and DTA curves of Co-ZIF-67.\u003c/p\u003e","description":"","filename":"2.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/5f80614008bc02b01a2f196e.jpg"},{"id":91955981,"identity":"19b305d0-d484-48fb-acef-4d9d588ec855","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":82564,"visible":true,"origin":"","legend":"\u003cp\u003eWater molecules in the cavity of Co-ZIF-67 (crystal 1).\u0026nbsp; 8 water molecules per unit cell are occupied by H\u003csub\u003e2\u003c/sub\u003eO (opposite of 6-rings in the cavity of Co-ZIF-67) as shown.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/28ac8cbe27c137830bc4884a.png"},{"id":91955974,"identity":"64033821-68f9-4828-a6be-dc5da600ab24","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":225537,"visible":true,"origin":"","legend":"\u003cp\u003e(a) A water molecule at site O1 of opposite 6-ring in crystal 1. A water molecule interacted with C2 of the methyl groups of the three ligands. (b) A water molecule at site O2 of opposite 6-ring in crystal 1. A water molecule interacted with C2 of the methyl groups of the three ligands.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/fb1cbf74ae7bae64edac8255.png"},{"id":91955976,"identity":"ac4ba7cc-9805-4618-b0bf-ac8eccfdfbce","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":78595,"visible":true,"origin":"","legend":"\u003cp\u003eStructure of fully dehydrated Co-ZIF-67 in crystals 2 to 10\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/5227b272374e23e1b648f8f8.png"},{"id":91956777,"identity":"1610b848-7661-4a32-9e1c-96b2e1dfec84","added_by":"auto","created_at":"2025-09-23 07:18:38","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":93370,"visible":true,"origin":"","legend":"\u003cp\u003e(a) The number of C3 per unit cell with increasing heating temperature (b) The number of C3 per unit cell with increasing time at 683K\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/ee8dd64095ef9ee2075bc415.png"},{"id":91956775,"identity":"7f33ad48-6dac-4c77-b621-f481e56141f8","added_by":"auto","created_at":"2025-09-23 07:18:38","extension":"jpg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":27984,"visible":true,"origin":"","legend":"\u003cp\u003eStructure of Co/Zn-ZIF-67 in crystals 11 to 13\u003c/p\u003e","description":"","filename":"7.jpg","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/3e429648935af8d5f36b5abd.jpg"},{"id":91955983,"identity":"610c0875-626d-4762-b3cc-5ff47914b5cc","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":55665,"visible":true,"origin":"","legend":"\u003cp\u003eAperture size of Co-ZIF-67 in crystals 1 to 13\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/cb962528d32b3ca203daa9de.png"},{"id":96650145,"identity":"648cb81d-9555-4039-a4a5-0f7a3c3f379c","added_by":"auto","created_at":"2025-11-24 16:08:42","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2917406,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/eaf08bde-d5f7-470a-a2aa-57e32c1c7d81.pdf"},{"id":91955982,"identity":"6c5a28b5-2029-404d-9ae5-e11e383022c9","added_by":"auto","created_at":"2025-09-23 07:10:38","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":571914,"visible":true,"origin":"","legend":"","description":"","filename":"ZIF67WTLv1.1SupportingMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-7579437/v1/d85dbc3be64b94ac6cf010c9.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Fine-Tuning the Aperture Size of Co-ZIF-67 via Dehydration, Demethylation, and Co-Zn Hybridization","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eZeolitic imidazolate frameworks (ZIFs), a unique subclass of porous metal organic frameworks (MOFs) with a sodalite-type cage similar to zeolite topology, consist of transition metal ions such as zinc and cobalt and imidazolate linkers forming 3D tetrahedral frameworks [\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6 CR7 CR8 CR9\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. Hence, they have unique properties by combining the advantages of zeolites and MOF materials such as high surface area, high crystallinity, exceptional thermal and chemical stability, and abundant active sites [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. These properties make ZIFs promising candidate for many applications such as gas storage and separation, medicine, catalysis, and sensor, etc. [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eIn general, ZIFs with different structures and properties can be achieved by tuning the type of metal ions and organic linker to control the shape, the size, and the pore [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. Accordingly, over a hundred unique structures for ZIFs have been extensively studied and synthesized to date by the choice of metal ions and functionalization of the imidazolate linkers [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan additionalcitationids=\"CR11 CR12 CR13 CR14 CR15\" citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eAs one of ZIFs, Co-ZIF-67 consists of cobalt ions as metal nodes and 2-methylimidazolate anions as the organic linker, and forms a sodalite-type cage with a pore size of about 0.34 nm which is similar to the zeolite\u0026rsquo;s topology [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. It is relatively easy to synthesize compared to other materials and has excellent thermal and chemical stability, high hydrophobicity, high porosity, and a large specific surface area which are favorable for the adsorption reactions due to its strong affinity for guest molecules [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. Accordingly, Co-ZIF-67 has been shown to have excellent activity for many guest molecules in various applications as gas storage and separation including volatile organic compounds adsorption and separation [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. In general, the gas adsorption properties of the Co-ZIF-67 are strongly influenced by the distribution of water molecules and demethylation of the 2-methylimidazolate ligands in the framework of ZIFs because the size of the pores changes and the type of gas that can be separated changes, when the water molecules are removed and demethylation occurs by thermal treatment [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Furthermore, Co-ZIF-67 is very sensitive to moisture and is unstable in an aqueous solution or water [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. According to previous reports, although Co-ZIF-67 has exhibited high adsorption ability for various gases, its adsorption ability significantly decreases when exposed to moisture under ambient conditions. Moreover, adsorption ability is drastically reduced after immersion in water due to the collapse of the crystal structure [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e]. Therefore, the water sensitivity and demethylation of Co-ZIF-67 are key parameters for its application in commercial settings. However, to the best of our knowledge, despite previous efforts in studies on the adsorption applications of Co-ZIF-67, detailed information about the chemical and thermal stability in the presence moisture at ambient conditions is still not fully understood or very limited. Here, for development of gas separation, we investigate the behavior of water molecules in the framework of Co-ZIF-67 by increasing heating temperature under vacuum more precisely and also show the framework structure of demethylation on the 2-methylimidazolate ligands in Co-ZIF-67 at specific temperatures. Finally, we want to observe the change in the aperture size of the 6-ring when complete dehydration and demethylation occurs.\u003c/p\u003e\u003cp\u003eIn general, most ZIF structures studied are based on single metals, and their properties (surface area, aperture sizes, porosity, thermal stability and so on) primarily depend on the metal species [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. In particular, the gas diffusion properties of isostructural ZIFs with different metal centers depend on both their crystallographically-defined aperture sizes with different metal and the stiffness of the corresponding metal-nitrogen [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Accordingly, by precisely controlling the metal substitution in Co-ZIF-67, one can potentially fine-tune its effective aperture sizes, which has significant implications for gas separation applications.\u003c/p\u003e\u003cp\u003eAccording to the previous reports, the dual metallic Zn/Co-ZIF by tuning the amount of Co and Zn has different physical properties (surface area, aperture sizes, porosity, thermal stability, and so on) and chemical properties (CO\u003csub\u003e2\u003c/sub\u003e-TPD, NH\u003csub\u003e3\u003c/sub\u003e-TPD) compared with single metal ZIFs [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. Therefore, the construction of mixed metal-ZIF would be a fascinating option that provides an effective way to tune or introduce new properties in ZIFs [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. For this reason, mixed metal-ZIFs have been extensively studied and synthesized in recent years, but the direct synthesis and characterization of mixed metal-ZIFs seem to be still challenging [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Herein, we synthesize single crystals of Co/Zn Hybrid ZIF-67 (hereafter, Co/Zn-ZIF-67) and investigate the property changes of Co-ZIF-67 through crystal structure analysis. This detailed information could provide new insights into the practical application of Co/Zn-ZIF-67 in gas adsorption, gas separation, and catalysis.\u003c/p\u003e\u003cp\u003eIn the present work, the large single crystal of Co-ZIF-67 was successfully synthesized through the facile hydrothermal method and fully characterized by systematic physical and chemical measurements such as single-crystal synchrotron X-ray diffraction technique, scanning electron microscope, and thermal gravimetric and differential thermal analysis. Based on these results, the properties of the Co-ZIF-67 were also compared with those of Zn-ZIF-8. In addition, large single crystals of Co/Zn-ZIF-67 with various Co/Zn ratios were synthesized, showing that Zn substitution can potentially tune the aperture size of ZIF-67.\u003c/p\u003e"},{"header":"2. Experimental Section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\u003ch2\u003e2.1. Synthesis of Large Single Crystal of Co-ZIF-67\u003c/h2\u003e\u003cp\u003eThe chemicals used for synthesizing included cobalt nitrate hexahydrate (Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO, Alfa Acesar), 2-methylimidazole (C\u003csub\u003e4\u003c/sub\u003eH\u003csub\u003e6\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003e, Sigma Aldrich), methanol (CH\u003csub\u003e4\u003c/sub\u003eO, Sigma Aldrich), dimethylformamide (C\u003csub\u003e3\u003c/sub\u003eH\u003csub\u003e7\u003c/sub\u003eNO, Jun Sei), and nitric acid (HNO\u003csub\u003e3\u003c/sub\u003e, Sam Jung). All the chemical reagents were used without further purification. Large single crystal of ZIF-67 was prepared by following the recopied by Kwon \u003cem\u003eet al\u003c/em\u003e. with a slight modification [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. In a typical synthesis, 1.05 g of cobalt nitrate hexahydrate and 0.27 g 2-methylimidazole were dissolved in 108 mL of dimethylformamide containing six drops of 1 M nitric acid and stirred vigorous for 10 min. Above solution was transferred into a 250 mL glass bottle kept in an oven at 403 K for 144 h. After the reaction, the glass bottle was naturally cooled down to room temperature and the product was washed with methanol by sonication several times. Then, it was dried at 323 K for 12 h.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\u003ch2\u003e2.2. Dehydration, Demethylation, and Decomposition\u003c/h2\u003e\u003cp\u003eEach of 10 Co-ZIF-67 single crystals was lodged in a Pyrex capillary. Crystal 1 was as-synthesized without any thermal treatment and the capillary containing the crystal was sealed with a torch to block from the outside air. Crystals 2 to 8 were attached to a vacuum system, and the crystals were thermal treated at 673, 683, 688, 693, 698, 703, and 723 K, respectively, under dynamic vacuum for 48 h (see Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). Crystals 9 and 10 were thermally treated ZIF-67 at 683 K under dynamic vacuum for 48 and 54 h, respectively (see Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). The crystal in each capillary was sealed off under vacuum from the line.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\u003ch2\u003e2.3. Synthesis of Large Single Crystal of Co/Zn-ZIF-67\u003c/h2\u003e\u003cp\u003eMixed-metal Co/Zn-ZIF-67 single crystals were synthesized based on the Co-ZIF-67 synthesis protocol described above, with slight modifications using the molar ratio of Co to Zn in the synthesis solution (Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO : Zn((NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) at 1:3, 1:1, and 3:1, respectively, in the presence of the ligand solution (2-methylimidazole). After mixing the metal precusors, including both cobalt salt and zinc salt, with the ligand solution, the mixture was transferred into a 250 mL glass bottle and heated in an oven at 403 K for 144 h. After the reaction, the glass bottle was naturally cooled down to room temperature and the product was washed with methanol by sonication several times. Then, it was dried at 323 K for 12 h.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\u003ch2\u003e2.4. Characterization\u003c/h2\u003e\u003cp\u003eThe morphology, size, and purity of the synthesized Co-ZIF-67 and Co/Zn-ZIF-67 single-crystals were characterized using scanning electron microscope (SEM, Tescan VEGA II LMU). Scanning electron microscope-energy dispersive X-ray (SEM-EDX) analysis was done to determine the compositions of Co/Zn-ZIF-67. A comparison of the compositions as determined by crystallographic data and SEM-EDX analysis is presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e. Thermal gravimetric analysis (TGA) and differential thermal analysis (DTA) measurements were performed by thermal analyzer (TG-DTA, Rigaku TG-DTA 8122). For this purpose, \u003cem\u003eca.\u003c/em\u003e10 mg samples were filled into an alumina crucible and heated in a continuous-flow of nitrogen gas with a ramp rate of 10 ℃/min from 313 to 773 K.\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003eCrystal composition (at %) by crystallographic (SXRD) and SEM-EDX analyses for crystals 11, 12, and 13\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"7\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\" morerows=\"1\" rowspan=\"2\"\u003e\u003cp\u003eElement\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c3\" namest=\"c2\"\u003e\u003cp\u003eCrystal 11\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c5\" namest=\"c4\"\u003e\u003cp\u003eCrystal 12\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colspan=\"2\" nameend=\"c7\" namest=\"c6\"\u003e\u003cp\u003eCrystal 13\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eSXRD\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u003cp\u003eSEM-EDX\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003eSXRD\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003eSEM-EDX\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003eSXRD\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c7\"\u003e\u003cp\u003eSEM-EDX\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e5.32\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e5.11\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e4.81\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e4.56\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e6.03\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e5.96\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eZn\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e2.37\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e2.33\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e2.88\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e3.24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e1.67\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e1.55\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eN\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e30.77\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e29.25\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e30.77\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e29.09\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e30.77\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e29.46\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e\u003cp\u003e61.54\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e\u003cp\u003e63.31\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e\u003cp\u003e61.54\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e\u003cp\u003e63.11\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e\u003cp\u003e61.54\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"char\" char=\".\" colname=\"c7\"\u003e\u003cp\u003e63.03\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003ctfoot\u003e\u003ctr\u003e\u003ctd colspan=\"7\"\u003e\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003eOnly Co, Zn, N, and C were found in these crystals. \u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003eThe ZIF crystal can be expected to have suffered some decomposition upon exposure to the atmosphere and the action of the electron beam. This can be a significant source of error.\u003c/td\u003e\u003c/tr\u003e\u003c/tfoot\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec7\" class=\"Section2\"\u003e\u003ch2\u003e2.5. X-ray Diffraction.\u003c/h2\u003e\u003cp\u003eDiffraction data were collected for the thirteen crystals using synchrotron X-radiation. Temperature was maintained at 100(1) K by a flow of cold nitrogen gas. Preliminary cell constants and an orientation matrix were determined from 72 sets of frames collected at scan intervals of 5\u003csup\u003eo\u003c/sup\u003e with an exposure time of 1 s per frame. The basic scale file was prepared using the HKL3000 program [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. The reflections were successfully indexed by the automated indexing routine of the DENZO program [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. The diffraction data were harvested by collecting 72 sets of frames with 5\u003csup\u003eo\u003c/sup\u003e scans with an exposure time of 1 s per frame. These highly redundant data sets were corrected for Lorentz and polarization effects, and a very small correction for crystal decay was applied. The space group \u003cem\u003eI\u003c/em\u003e\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\:\\stackrel{-}{4}\\)\u003c/span\u003e\u003c/span\u003e3\u003cem\u003em\u003c/em\u003e, standard for ZIF-67, was determined by the program XPREP [\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e]. A summary of the experimental and crystallographic data with some additional details is presented in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e.\u003c/p\u003e\u003c/div\u003e"},{"header":"3. Structure Determination","content":"\u003cp\u003eFull-matrix least-squares refinement (SHELXL2014) was done on \u003cem\u003eF\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e using all data for each crystal [\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Each initial refinement used anisotropic thermal parameters and converged to the high error indices.\u003c/p\u003e\u003cp\u003eFixed weights were used initially; the final weights were assigned using the formula \u003cem\u003ew\u003c/em\u003e\u0026thinsp;=\u0026thinsp;1/[σ\u003csup\u003e2\u003c/sup\u003e(\u003cem\u003eF\u003c/em\u003e\u003csub\u003eo\u003c/sub\u003e\u003csup\u003e2\u003c/sup\u003e) + (\u003cem\u003eaP\u003c/em\u003e)\u003csup\u003e2\u003c/sup\u003e + \u003cem\u003ebP\u003c/em\u003e] where \u003cem\u003eP\u003c/em\u003e = [Max(\u003cem\u003eF\u003c/em\u003e\u003csub\u003eo\u003c/sub\u003e\u003csup\u003e2\u003c/sup\u003e,0)\u0026thinsp;+\u0026thinsp;2\u003cem\u003eF\u003c/em\u003e\u003csub\u003ec\u003c/sub\u003e\u003csup\u003e2\u003c/sup\u003e]/3; the refined values of \u003cem\u003ea\u003c/em\u003e and \u003cem\u003eb\u003c/em\u003e are given in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. Neutral atomic scattering factors within SHELX-2014 were used, and all were modified to account for anomalous dispersion [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e, \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. All non-hydrogen atoms were refined using anisotropic thermal parameters. Hydrogen atoms were included in the structure factor calculation at idealized positions by using riding model. The final error indices are given in Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e. The structural parameters are given in Table S2 and selected interatomic distances and angles can be found in Table S3.\u003c/p\u003e"},{"header":"4. Results","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\u003ch2\u003e4.1. Morphology characteristic of Co-ZIF-67\u003c/h2\u003e\u003cp\u003eWe have first used optical microscope (OM) for confirming the synthesis of large single crystal Co-ZIF-67 and Co/Zn-ZIF-67. Similar to the previously reported Co-ZIF-67, we found that the product was pure-phase ZIF-67 materials with polyhedral shape and purple color (see Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e1\u003c/span\u003e(a)). The Co-ZIF-67 is a deep purple in color whereas Co/Zn-ZIF-67 is light purple. The SEM images of Co-ZIF-67 were shown in Figs.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e1\u003c/span\u003e(b) and (c). It could be seen that all Co-ZIF-67 crystals have a large quantity of regular particles with uniform and well-defined dodecahedron with sharp edges and smooth faces as reported in previous studies [\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e, \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e, \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. In addition, as shown in the SEM images, the crystal sizes of Co/Zn-ZIF-67 (100\u0026ndash;200 ㎛) are decreased compared to those of Co-ZIF-67 (100\u0026ndash;300 ㎛). The presence of Co and Zn in Co/Zn-ZIF-67 single crystal were investigated by single-crystal X-ray diffraction techniques and SEM-EDX analysis, respectively (see Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, and Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e1\u003c/span\u003e (c)). The SEM-EDX analysis revealed that the Co content is higher than the Zn content in all Co/Zn-ZIF-67 single crystal which was in good agreement with the result of a crystallographic study (see Tables\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e and \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e\u003cp\u003e\u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e\u003ccaption language=\"En\"\u003e\u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e\u003cdiv class=\"CaptionContent\"\u003e\u003cp\u003ePositional, Thermal, and Occupancy Parameters\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003e of Crystals 1 to 13\u003c/p\u003e\u003c/div\u003e\u003c/caption\u003e\u003ccolgroup cols=\"14\"\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c7\" colnum=\"7\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c8\" colnum=\"8\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c9\" colnum=\"9\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c10\" colnum=\"10\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c11\" colnum=\"11\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c12\" colnum=\"12\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c13\" colnum=\"13\"\u003e\u003c/div\u003e\u003cdiv align=\"left\" class=\"colspec\" colname=\"c14\" colnum=\"14\"\u003e\u003c/div\u003e\u003cthead\u003e\u003ctr\u003e\u003cth align=\"left\" colname=\"c1\"\u003e\u003cp\u003eatom\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c2\"\u003e\u003cp\u003eWyckoff position\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/th\u003e\u003cth align=\"left\" colname=\"c4\"\u003e\u003cp\u003ex\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c5\"\u003e\u003cp\u003ey\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c6\"\u003e\u003cp\u003ez\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c7\"\u003e\u003cp\u003e\u003cem\u003eU\u003c/em\u003e\u003csub\u003e11\u003c/sub\u003e\u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003e or \u003cem\u003eU\u003c/em\u003e\u003csub\u003eiso\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c8\"\u003e\u003cp\u003e\u003cem\u003eU\u003c/em\u003e\u003csub\u003e22\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c9\"\u003e\u003cp\u003e\u003cem\u003eU\u003c/em\u003e\u003csub\u003e33\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c10\"\u003e\u003cp\u003e\u003cem\u003eU\u003c/em\u003e\u003csub\u003e23\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c11\"\u003e\u003cp\u003e\u003cem\u003eU\u003c/em\u003e\u003csub\u003e13\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c12\"\u003e\u003cp\u003e\u003cem\u003eU\u003c/em\u003e\u003csub\u003e\u003cem\u003e12\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c13\"\u003e\u003cp\u003eOccupancy\u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/th\u003e\u003cth align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/th\u003e\u003c/tr\u003e\u003c/thead\u003e\u003ctbody\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 1 (in situ Co-ZIF-67)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e655(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e655(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e638(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e12\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eN1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e898(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5332(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8176(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e687(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e661(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e684(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e18(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-30(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-23(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1233(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4935(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8767(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e675(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e635(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e675(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e8(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e6(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-8(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1864(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6041(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8698(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e790(14)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e675(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e821(15)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e72(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-91(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-90(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e955(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4144(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9045(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e808(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e713(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e808(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e82(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-10(16)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-88(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(\u003cem\u003ec\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1866(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e8134(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8134(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e2199(193)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e2199(193)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e2199(193)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e531(173)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-531(173)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-531(173)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e5.0(5)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(\u003cem\u003ec\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3194(36)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6806(36)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e6806(36)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e3083(783)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e3083(783)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e3083(783)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e-86(534)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e86(534)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e86(534)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e2.9(7)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH2\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e2218\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6446\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8798\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e913\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3a\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg)\u003c/em\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1395\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3791\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9074\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1164\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3b\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e573\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3941\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8681\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1164\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3c\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e720\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4195\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9557\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1164\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 2 (fully dehydrated at 673 K)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e612(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e612(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e594(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e12\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eN1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e901(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5322(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8171(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e668(18)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e593(15)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e651(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e21(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-59(15)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-60(14)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1228(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4939(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8772(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e676(16)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e614(32)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e676(16)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e27(23)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e26(20)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-27(23)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1873(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6022(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8684(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e751(26)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e644(21)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e788(25)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e45(19)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-66(19)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-76(19)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e940(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4150(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9060(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e759(21)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e726(35)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e759(21)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e75(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-111(31)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-75(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH2\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e2231\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6426\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8776\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e873\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3a\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg)\u003c/em\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1258\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3981\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9796\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1122\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3b\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e401\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4200\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9226\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1122\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3c\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e978\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3772\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8642\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1122\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 3 (dehydrated at 683 K)\u003c/b\u003e\u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e937(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4147(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9067(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1055(64)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e866(97)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1055(64)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e137(49)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-107(72)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-137(49)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e23.6(5)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 4 (dehydrated at 688 K)\u003c/b\u003e\u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e927(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4150(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9073(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1175(135)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-309(84)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e1205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e23.4(6)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 5 (dehydrated at 693 K)\u003c/b\u003e\u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e927(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4150(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9073(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1175(135)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-309(84)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e1205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e23.0(6)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 6 (dehydrated at 698 K\u003c/b\u003e \u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e934(7)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4162(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9066(7)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1423(107)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1363(217)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1422(107)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e137(103)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-241(112)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-137(103)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e22.6(4)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 7 (dehydrated at 703 K)\u003c/b\u003e\u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e927(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4150(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9073(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1175(135)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-309(84)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e1205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e22.9(3)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 8 (dehydrated at 723 K)\u003c/b\u003e\u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e927(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4150(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9073(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1175(135)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1301(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-309(84)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e1205(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e23.1(8)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 9 (dehydrated at 683 K for 54 h)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1032(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1039(11)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e977(15)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e12\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eN1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e900(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5317(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8168(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e991(58)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1073(70)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1064(53)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e112(48)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-129(41)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-112(43)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1235(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4932(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8765(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1019(54)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e833(101)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1019(54)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e-47(76)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e35(83)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e47(76)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1313(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6011(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8128(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1303(72)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1035(68)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1302(77)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e202(54)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-195(58)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-204(57)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e930(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4151(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9070(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1253(85)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e1064(148)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1253(85)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e181(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-320(93)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-181(74)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e22.3(4)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH2\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1219\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6418\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7768\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1456\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3a\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg)\u003c/em\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e399\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4218\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9265\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1785\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3b\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1265\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3969\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9492\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1785\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3c\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e931\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3770\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8649\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1785\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 10 (dehydrated at 683 K for 60 h)\u003c/b\u003e\u003csup\u003e\u003cb\u003ee\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e934(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4147(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9066(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1152(63)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e916(87)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e1152(63)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e172(49)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-200(73)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-172(49)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e\u003cb\u003e19.3(11)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 11 (Co/Zn-ZIF-67, no dehydrated)\u003c/b\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e71(5)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4935(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7558(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e389(25)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e8.3(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eZn1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e284(123)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e284(123)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e329(115)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e3.7(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eN1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e893(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5345(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8177(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e543(11)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e549(11)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e566(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e18(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-44(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-22(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1236(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4934(4)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8764(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e545(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e480(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e545(9)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e2(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e22(11)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-2(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1845(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6063(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8714(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e715(18)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e545(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e682(17)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e63(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-88(14)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-123(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e48\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eC3\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e972(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4135(3)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9028(2)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e705(15)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e554(19)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e705(15)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e79(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e-137(19)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e-79(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e24\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(c)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1923(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e8077(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8077(12)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1363(92)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e3.9(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(c)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3209(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6791(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e6791(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e2823(346)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e4.1(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH2\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e48(\u003cem\u003eh\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e2191\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6477\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8821\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e777\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3a\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg)\u003c/em\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1303\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3957\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9453\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e981\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3b\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e434\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4163\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e9207\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e981\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eH3c\u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e24(\u003cem\u003eg\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1008\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e3771\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8595\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e981\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 12 (Co/Zn-ZIF-67, no dehydrated)\u003c/b\u003e \u003csup\u003e\u003cb\u003ef\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e84\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4926(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7574(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e363(36)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e7.5(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eZn1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e470(90)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e470(90)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e494(87)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e4.5(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(c)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1901(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e8099(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8099(10)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1699(91)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e6.1(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(c)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3335(38)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6665(38)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e6665(38)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e3038(373)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e1.9(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colspan=\"14\" nameend=\"c14\" namest=\"c1\"\u003e\u003cp\u003e\u003cb\u003ecrystal 13 (Co/Zn-ZIF-67, no dehydrated)\u003c/b\u003e \u003csup\u003e\u003cb\u003ef\u003c/b\u003e\u003c/sup\u003e\u003c/p\u003e\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eCo1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e74(6)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e4939(7)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7564(8)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e488(22)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e9.4(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eZn1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e12(\u003cem\u003ed\u003c/em\u003e)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e5000\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e7500\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e346(135)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u003cp\u003e346(135)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u003cp\u003e330(198)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u003cp\u003e0\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e2.6(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO1\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(c)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e1936(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e8064(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e8064(13)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1149(92)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e4.9(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003ctr\u003e\u003ctd align=\"left\" colname=\"c1\"\u003e\u003cp\u003eO2\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c2\"\u003e\u003cp\u003e8(c)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c4\"\u003e\u003cp\u003e3161(32)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c5\"\u003e\u003cp\u003e6839(32)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c6\"\u003e\u003cp\u003e6839(32)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c7\"\u003e\u003cp\u003e1785(332)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c8\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c9\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c10\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c11\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c12\"\u003e\u0026nbsp;\u003c/td\u003e\u003ctd align=\"left\" colname=\"c13\"\u003e\u003cp\u003e3.1(1)\u003c/p\u003e\u003c/td\u003e\u003ctd align=\"left\" colname=\"c14\"\u003e\u0026nbsp;\u003c/td\u003e\u003c/tr\u003e\u003c/tbody\u003e\u003c/colgroup\u003e\u003ctfoot\u003e\u003ctr\u003e\u003ctd colspan=\"14\"\u003e\u003csup\u003e\u003cem\u003ea\u003c/em\u003e\u003c/sup\u003ePositional and thermal parameters \u0026times; 10\u003csup\u003e4\u003c/sup\u003e are given. Numbers in parentheses are the esds in the units of the least significant figure given for the corresponding parameter. \u003csup\u003e\u003cem\u003eb\u003c/em\u003e\u003c/sup\u003eThe anisotropic temperature factor is exp[-2π\u003csup\u003e2\u003c/sup\u003e\u003cem\u003ea\u003c/em\u003e\u003csup\u003e\u0026minus;2\u003c/sup\u003e(\u003cem\u003eU\u003c/em\u003e\u003csub\u003e11\u003c/sub\u003e\u003cem\u003eh\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;+\u0026thinsp;\u003cem\u003eU\u003c/em\u003e\u003csub\u003e22\u003c/sub\u003e\u003cem\u003ek\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e\u0026thinsp;+\u0026thinsp;\u003cem\u003eU\u003c/em\u003e\u003csub\u003e33\u003c/sub\u003e\u003cem\u003el\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e + 2\u003cem\u003eU\u003c/em\u003e\u003csub\u003e23\u003c/sub\u003e\u003cem\u003ekl\u003c/em\u003e\u0026thinsp;+\u0026thinsp;2\u003cem\u003eU\u003c/em\u003e\u003csub\u003e13\u003c/sub\u003e\u003cem\u003ehl\u003c/em\u003e\u0026thinsp;+\u0026thinsp;2\u003cem\u003eU\u003c/em\u003e\u003csub\u003e12\u003c/sub\u003e\u003cem\u003ehk\u003c/em\u003e)]. \u003csup\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sup\u003eThe Occupancy factor is given as the number of atoms. \u003csup\u003e\u003cem\u003ed\u003c/em\u003e\u003c/sup\u003eHydrogen atom positions were calculated by the suite of computer programs SHELXL-2017. \u003csup\u003e\u003cem\u003ee\u003c/em\u003e\u003c/sup\u003eThe framework atoms (Co,N, C(C1 and C2), and H) were omitted to avoid the repetition of similar data. \u003csup\u003e\u003cem\u003ef\u003c/em\u003e\u003c/sup\u003eThe framework atoms (N, C, and H) were omitted to avoid the repetition of similar data.\u003c/td\u003e\u003c/tr\u003e\u003c/tfoot\u003e\u003c/table\u003e\u003c/div\u003e\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\u003ch2\u003e4.2. Thermal stability of ZIF-67\u003c/h2\u003e\u003cp\u003eThe thermal stability of Co-ZIF-67 crystals was evaluated by TG-DTA analysis under an N\u003csub\u003e2\u003c/sub\u003e atmosphere. The result of TG-DTA of Co-ZIF-67 crystal with increasing temperature was shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e2\u003c/span\u003e. Similar to the previously reported Co-ZIF-67, the TGA curve shows a slight initial weight loss of 3.2% for Co-ZIF-67 between 300 and 523 K, which is attributed to the removal of guest molecules and unreacted species [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. Subsequently, a significant weight loss of Co-ZIF-67 was observed in the temperature range of 523\u0026thinsp;~\u0026thinsp;773 K due to the decomposition of organic ligands and the collapse of the framework corresponding to the exothermic peak in the DTA curve, which is a good agreement with the several previous TGA studies on Co-ZIF-67 [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e].\u003c/p\u003e\u003c/div\u003e"},{"header":"5. Description of the Structures","content":"\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\u003ch2\u003e5.1. Framework of Co-ZIF-67\u003c/h2\u003e\u003cp\u003eCo-ZIF-67 has eight single 6-rings and four single 4-rings like sodalite zeolite (see Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003e). The average distance Co, the central metal, and N of imidazolate, the organic ligand, was 1.99 \u0026Aring;, which was observed similar to the known distance (see Table S3). The N1\u0026ndash;Co\u0026ndash;N1 bond angle is almost 109.5\u0026deg;, nearly perfectly tetrahedral (see Table S3). The average distances between the atoms in the organic ligands forming the structure were 1.34, 1.36, and 1.51 \u0026Aring; for N1\u0026ndash;C1, N1\u0026ndash;C2, and C1\u0026ndash;C3, respectively (see Table S3). These are similar to those of the single-crystal structure of 2-methylimidazole [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e].\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec14\" class=\"Section2\"\u003e\u003ch2\u003e5.2. Structure of Crystal 1.\u003c/h2\u003e\u003cp\u003eIn the structure of crystal 1, 8 water molecules per unit cell were found in two crystallographic sites (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, S2, Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003e, and \u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e4\u003c/span\u003e). The 5.0(5) water molecules per unit cell at O1 were located opposite 6-rings in the cavity of Co-ZIF-67 (see Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e4\u003c/span\u003e(a)). Each water molecule at O1 is recessed \u003cem\u003eca\u003c/em\u003e. 1.827 \u0026Aring; into the cavity from their plan. The remaining 2.9(7) water molecules per unit cell at O2 were located opposite 6-rings outside the cavity of Co-ZIF-67 (see Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e4\u003c/span\u003e(b)). Each water molecule at O2 extends out of the cavity \u003cem\u003eca\u003c/em\u003e. 1.999 \u0026Aring; from its Co plane (see Table S3). The water molecules at O1 and O2 were interacting with the hydrogens of the C-C bonds of three ligands on the 6-ring plane (see Fig.\u0026nbsp;\u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e4\u003c/span\u003e). These distances between the water molecules at O1 and O2 and the hydrogen of ligand, O1\u0026ndash;H2 and O2\u0026ndash;H2, were 3.119 and 3.786 \u0026Aring;, respectively (see Table S3). In this structure, water molecules were fully occupied at 6-ring planes (see Figs.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e3\u003c/span\u003e and \u003cspan refid=\"Fig12\" class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e\u003ch2\u003e5.2. Structure of Crystal 2.\u003c/h2\u003e\u003cp\u003eCrystal 2 was thermally treated Co-ZIF-67 at 673 K under a dynamic vacuum of 6.5 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e Pa for 48 h. In this structure, no water molecules were found (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, S2, and Fig.\u0026nbsp;\u003cspan refid=\"Fig13\" class=\"InternalRef\"\u003e5\u003c/span\u003e). The 8 water molecules per unit cell at O1 and O2 in the structure of crystal 1 were completely removed when treated at 673 K under a dynamic vacuum of 6.5 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e Pa. Despite complete dehydration, this structure retained its crystallinity without any signs of crystal decomposition.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec16\" class=\"Section2\"\u003e\u003ch2\u003e5.3. Structures of Crystal 3\u0026ndash;8.\u003c/h2\u003e\u003cp\u003eCrystals 3\u0026ndash;8 were thermally treated at 683, 688, 693, 698, 703, and 723 K, respectively, under a dynamic vacuum for 48 h. There were no water molecules in the structures of crystals 3\u0026ndash;8 as in the structure of crystal 2. However, the occupancy of methyl group at C3 of the 2-methylimidazolate ligands per unit cell in Co-ZIF-67 was decreased slightly as the heating temperature increased (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, Table S2 and Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e6\u003c/span\u003e(a)). The occupancy of methyl group at C3 of the ligands per unit cell in the structure of crystals 3\u0026ndash;8 were 23.6(5), 23.4(6), 23.0(6), 22.6(4), 22.9(3), and 23.1(8), respectively (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Table S2). It is noted that, no single-crystal X-ray diffraction data were obtained at 753 K due to the loss of crystallinity of Co-ZIF-67.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec17\" class=\"Section2\"\u003e\u003ch2\u003e5.4. Structure of Crystals 9 and 10.\u003c/h2\u003e\u003cp\u003eThe crystal 9 and 10 were thermally treated with heating times of 54 and 60 h, respectively, at 683 K under a dynamic vacuum of 6.2 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e Pa. In these structures, as in crystals 3 to 8, no water molecules were present. The occupancy of methyl group at C3 of the 2-methylimidazolate ligands per unit cell in ZIF-67 was decreased as the heating time increased (see Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e6\u003c/span\u003e(b)). The occupancies of methyl group at C3 of the ligands per unit cell in the structure of crystal 9 and 10 were 22.3(4) and 19.3(11), respectively (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and S2).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec18\" class=\"Section2\"\u003e\u003ch2\u003e5.5. Structures of Crystal 11\u0026ndash;13.\u003c/h2\u003e\u003cp\u003eThe crystals 11, 12, and 13 were synthesized with Co/Zn molar ratios of 1:3, 1:1, and 3:1, respectively, in the synthesis solution. The Co/Zn-ZIF-67 has a tetrahedral structure because each metal center coordinates with four nitrogen atoms of four discrete ligands (see Fig.\u0026nbsp;\u003cspan refid=\"Fig15\" class=\"InternalRef\"\u003e7\u003c/span\u003e). This is similar as in the crystal structure of Co-ZIF-67. However, it is important to note that in the bimetallic M-ZIF framework, M can represent either Zn or Co, and its position within the crystal structure is completely random. Furthermore, the Co/Zn ratio in the ZIF framework is significantly influenced by the Co/Zn ratio employed during synthesis.\u003c/p\u003e\u003cp\u003eThe occupancies of Co and Zn per unit cell were 8.3 and 3.7 in crystal 11, 7.5 and 4.5 in crystal 12, and 9.4 and 2.6 in crystal 13, respectively (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Table S2). The Co contents are higher than the Zn contents in all three crystals. This preferential inclusion of Co ions is possibly attributed to the use of the Co-ZIF-67 synthesis method. The average distances between Co, the central metal, and the N of imidazolate were 1.9852, 1.9864, and 2.0101 \u0026Aring; for crystal 11, 12, and 13, respectively, whereas the average distances between Zn and N were 1.9830, 1.9834, and 1.9779 \u0026Aring; in crystal 11, 12, and 13, respectively (see Table S3).\u003c/p\u003e\u003cp\u003eIn all three crystals, water molecules at O1 and O2 were located opposite 6-rings in the cavity of Co/Zn-ZIF-67. The occupancies of water molecules at O1 and O2 per unit cell were 3.9 and 4.1 in crystal 11, 6.1 and 1.9 in crystal 12, and 4.9 and 3.1 in crystal 13, respectively (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e and Table S2). The water molecules at O1 and O2 were interacting with the hydrogen atom bonded to six carbon atoms of the ligand at C2 on the 6-ring plane. The positions and bonding distances of water molecules to framework are similar to those in crystal 1.\u003c/p\u003e\u003c/div\u003e"},{"header":"6. Discussion","content":"\u003cdiv id=\"Sec20\" class=\"Section2\"\u003e\u003ch2\u003e6.1. Water Molecules in Co-ZIF-67\u003c/h2\u003e\u003cp\u003eThe behavior of water molecules in the structures of Co-ZIF-67 treated at different temperatures under a dynamic vacuum can be seen from the crystallographic results of crystal 1 and 2.\u003c/p\u003e\u003cp\u003eThe water molecules in the structure of Co-ZIF-67 are \u003cem\u003eca.\u003c/em\u003e 8 per unit cell at the near center of the 6-ring planes as seen in the crystal 1 without any treatment. The water molecules in the structure of Co-ZIF-67 are likely to come from the reagent such as Cobalt nitrate hexahydrate (Co(NO\u003csub\u003e3\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e\u0026middot;6H\u003csub\u003e2\u003c/sub\u003eO) used in its synthesis. The water molecules were completely removed at 673 K without the loss of crystallinity as seen in the structure of crystal 2. The unit cell constants were not significantly changed by complete dehydration in the framework of Co-ZIF-67 (see Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). As a result of measuring the aperture size of the 6-ring, it was found that the aperture size of 5.824 \u0026Aring; in crystal 2 was smaller than that in crystal 1 (5.840 \u0026Aring;) due to the removal of water molecules from the 6-ring (see Table S4).\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec21\" class=\"Section2\"\u003e\u003ch2\u003e6.2. Demethylation of ZIF-67.\u003c/h2\u003e\u003cp\u003eGenerally, the demethylation should occur first before the breaking of Co-N coordination bond and C\u0026ndash;C bonds of the imidazolate ligand, because the C\u0026ndash;C bond between the imidazolate ring and the methyl group is relatively weak compared with the Co\u0026ndash;N coordination bond and the other bonds of the imidazolate ligand [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eIn this work, when heated at 673 K for 48 h (crystal 2) under a dynamic vacuum of 6.5 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e Pa, Co-ZIF-67 crystal showed no demethylation of the 2-methylimidazolate ligands despite complete dehydration. However, when thermally treated at 683 K for 48 h (crystal 3) under a dynamic vacuum of 6.5 \u0026times; 10\u003csup\u003e\u0026minus;\u0026thinsp;6\u003c/sup\u003e Pa, the occupancy of carbon of the methyl group at C3 of the 2-methylimidazolate ligands began to decrease in this crystal, indicating demethylation. As the heating temperature increased from 683 to 723 K, the number of carbons of the methyl group at C3 of the 2-methylimidazolate ligands in Co-ZIF-67 decreased slightly (see Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e, Table S2, and Fig.\u0026nbsp;\u003cspan refid=\"Fig14\" class=\"InternalRef\"\u003e6\u003c/span\u003e). The reduction percentages of the methyl group at C3 were 2%, 3%, 4%, 6%, 5%, and 4% at heating temperatures of 683, 688, 693, 698, 703, and 723 K under a dynamic vacuum, respectively. Additionally, the occupancy of the methyl group at C3 of the 2-methylimidazolate ligands was significantly decreased at 683 K with increasing heating time with 2%, 7%, and 20% for 48, 54, and 60 h, respectively. As a result of measuring the aperture size of the 6-ring, the aperture size in the heat-treated crystals tended to be larger than that in the untreated crystals (see Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e8\u003c/span\u003e). This result indicates that the systematic reduction of the methyl group, depending on the heating temperature and time under a dynamic vacuum, led to an increase in the aperture size of the structures, which can alter the type of gas separated during gas separation.\u003c/p\u003e\u003cp\u003eWhen a single crystal of Co-ZIF-67 was dehydrated at 753 K under a dynamic vacuum, no single-crystal X-ray diffraction data were obtained due to the loss of Co-ZIF-67 crystallinity. This result shows that the decomposition of ligands in Co-ZIF-67 is complete, which is consistent with previous TGA studies indicating that Co-ZIF-67 has thermal stability up to 673 K and is completely decomposed at temperatures higher than 723 K [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. The observation suggests that the remarkable thermal stability of Co-ZIF-67 allows it to be used in a variety of applications where relatively high temperatures are required.\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec22\" class=\"Section2\"\u003e\u003ch2\u003e6.3. Structural Comparison with Zn-ZIF-8 and Co-ZIF-67.\u003c/h2\u003e\u003cp\u003eZn-ZIF-8 and Co-ZIF-67 are formed by bridging 2-methylimidazolate with Zinc and Cobalt, respectively [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. They are iso-structural (\u003cem\u003ei.e\u003c/em\u003e., crystallographically same structure) with different metal nodes and have same crystallographic features such as crystal system and space group with similar lattice parameters. However, according to the previous studies, despite similar formation mechanisms, they have some different physical properties and chemical properties due to the difference in metal ions present in the imidazolate linker [\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e, \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eIn our previous crystallographic work, we have extensively studied the behavior of water molecules, demethylation, and decomposition of Zn-ZIF-8 upon thermal treatment [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. When the Zn-ZIF-8 [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e] and Co-ZIF-67 (in this work) are compared, it can be seen that there are some differences in the distribution of water molecules and the thermal stability with increasing temperature.\u003c/p\u003e\u003cp\u003eWhen the ZIFs are exposed to water, water molecules are located at three crystallographic sites on opposite 4-ring, near center of 6-ring plane, and between two 6-rings [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. Water molecule energetically preferred and the first to be filled in the 6-ring site, the remaining water molecules move to other sites under the increasing number of water molecules [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. These Water molecules are interacting with the hydrogen of the methyl group of the 2-methylimidazolate ligands [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e].\u003c/p\u003e\u003cp\u003eIn the structure of Zn-ZIF-8, water molecules occupy two crystallographic sites at opposite 4-ring and near center of 6-ring plane. However, in the structure of Co-ZIF-67, water molecules are located only one crystallographic site at near center of 6-ring plane. Unlike the structure of Zn-ZIF-8, no water molecules are found at opposite 4-ring, due to the relatively low content of water molecules in the structure of Co-ZIF-67.\u003c/p\u003e\u003cp\u003eWhen heated at 673 K for 48 h under a dynamic vacuum, the Co-ZIF-67 crystal showed complete dehydration but water molecules are not completely removed in the Zn-ZIF-8 crystal under the same condition, which is completely dehydrated at 723 K. In addition, the demethylation occurs first at 683 K under a dynamic vacuum in the Co-ZIF-67 crystal, whereas it occurs at 773 K under a dynamic vacuum in the Zn-ZIF-8 crystal. With increasing the heating temperature, the occupancy of the methyl group at C3 of the 2-methylimidazolate ligand is decreased in the both ZIF crystals. Subsequently, the thermal decomposition in the structure of the Co-ZIF-67 is observed at 753 K under a dynamic vacuum. On the other hand, unlike the structure of the Co-ZIF-67, the thermal decomposition in the structure of Zn-ZIF-8 is exhibited at 798 K under a dynamic vacuum. This result indicates that the thermal stability of the Co-ZIF-67 crystal is slightly lower than that of the Zn-ZIF-8 crystal as seen in previous work [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e]. It is strongly related to the coordination capability of Co ion to 2-methylimidazolate, which is weaker than that of Zn ion [\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e].\u003c/p\u003e\u003c/div\u003e\u003cdiv id=\"Sec23\" class=\"Section2\"\u003e\u003ch2\u003e6.4. Hybridization of Central Metal in ZIF-67\u003c/h2\u003e\u003cp\u003eIn this work, three types of Co/Zn-ZIF-67 single crystal with various Co/Zn ratios were synthesized to demonstrate the possibility of tuning the aperture size of Co-ZIF-67 by incorporating Zn centers. The structure and oxygen ion pattern of these crystals are shown to be similar to that of Co-ZIF-67 (crystal 1). However, the unit cell constants were significantly changed by incorporating Zn centers in the framework of Co-ZIF-67 (see Table \u003cspan refid=\"MOESM1\" class=\"InternalRef\"\u003eS1\u003c/span\u003e). Co/Zn-ZIF-67s (crystal 11, 12, and 13) have smaller unit cell parameters as compared to Co-ZIF-67 (crystal 1), which could be an effect of the smaller Zn\u0026ndash;N distance of the material. The distance of metal and N distance is an important factor for determining the crystallographically-defined aperture size [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Finally, as a result of measuring the aperture size of the 6-ring, the aperture sizes of the Co/Zn-ZIF-67s (5.795, 5.787, and 5.768 \u0026Aring; for crystal 11, 12, and 13, respectively) were smaller than that of the ZIF-67 (5.824 \u0026Aring; for crystal 1) (see Table S4 and Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e8\u003c/span\u003e). These findings indicate that the Co/Zn-ZIF-67 can tune the aperture size of the Co-ZIF-67 material for gas selectivity while maintaining the crystal structure of Co-ZIF-67 (see Fig.\u0026nbsp;\u003cspan refid=\"Fig16\" class=\"InternalRef\"\u003e8\u003c/span\u003e).\u003c/p\u003e\u003c/div\u003e"},{"header":"7. Summary","content":"\u003cp\u003eThe rhombic dodecahedral large single crystals of Co-ZIF-67 was successfully synthesized through the facile hydrothermal method and its structure was determined by single-crystal X-ray diffraction techniques. In the structure of Co-ZIF-67, about 8 water molecules were located only one crystallographic site at near center of 6-ring plane, these water molecules at O1 and O2 were completely removed at 673 K for 48 h under a dynamic vacuum. The demethylation was the first to occur at 683 K under a dynamic vacuum in Co-ZIF-67 crystal. With increasing heating temperature, the occupancy of the methyl group at C3 of the 2-methylimidazolate ligand was decreased with 2%, 3%, 4%, 6%, 5%, and 4% at 683, 688, 693, 698, 703, and 723 K, respectively. As a result of measuring the aperture size of the 6-ring, the aperture size in the heat-treated crystals tended to be larger than that in the untreated crystals. Single-crystal X-ray diffraction data could not be obtained at 753 K under a dynamic vacuum due to the loss of Co-ZIF-67 crystallinity. Additionally, single crystals of Co/Zn-ZIF-67 containing both Co and Zn center were successfully synthesized; their crystal structure closely resembles that of Co-ZIF-67. The percentages of Co and Zn in ZIF-67 depend on the Co/Zn ratio used during synthesis, and the Co content exceeds that of Zn in all three crystals. By incorporating Zn centers into the framework of Co-ZIF-67, the unit cell parameter and the aperture size of the Co/Zn-ZIF-67 are smaller than those of Co-ZIF-67. Consequently, dehydration, demethylation, and central-metal hybridization of Co-ZIF-67 with Zn offer promising approaches to fine-tuning its aperture sizes for gas adsorption and separation applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eHSK , GES, and WTL wrote the main manuscript text and HC prepared figures 1-3. All authors reviewed the manuscript.\u003c/p\u003e\u003ch2\u003eAcknowledgements\u003c/h2\u003e\u003cp\u003eThis research was supported by the Gyeongsangbuk-do RISE(Regional Innovation System \u0026amp; Education) project. The authors wish to thank the staff at Beamline 2D SMC at the Pohang Light Source, Korea, for assistance during data collection.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eC. Duan, Y. Yu, H. Hu, Green. Energy Environ. \u003cb\u003e7\u003c/b\u003e, 3 (2022)\u003c/span\u003e\u003c/li\u003e\u003cli\u003e\u003cspan\u003eX. Feng, M. 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Crystallogr. \u003cb\u003e40\u003c/b\u003e, 201 (2010)\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"journal-of-porous-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jopo","sideBox":"Learn more about [Journal of Porous Materials](http://link.springer.com/journal/10934)","snPcode":"10934","submissionUrl":"https://submission.nature.com/new-submission/10934/3","title":"Journal of Porous Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"ZIF-67, Demethylation, Dehydration, Single-crystal X-ray Diffraction","lastPublishedDoi":"10.21203/rs.3.rs-7579437/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-7579437/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eCo-ZIF-67 (Zeolitic Imidazolate Framework) is a porous material where cobalt (Co) metal ions bond with organic ligands through tetrahedral coordination. It exhibits high chemical and thermal stability similar to that of zeolite structures and is utilized for gas separation, making it an ideal target for research. A large single crystal of Co-ZIF-67 was successfully synthesized using a simple hydrothermal method. Dehydration and demethylation of the 2-methylimidazole in Co-ZIF-67, as well as altering the central metal, change the aperture size and affect the types of gases that can be separated. Therefore, in this work, dehydrated, demethylated, and hybridized Co-ZIF-67s with cobalt (Co) and zinc (Zn) were prepared in this work. These crystal structures were analyzed using single-crystal synchrotron X-ray diffraction techniques. In the untreated Co-ZIF-67 single crystal, water molecules were located at two sites opposite the 6-ring, with eight molecules per unit cell. Heat treatment at 673 K completely removed the water molecules without loss of crystallinity, and demethylation began at 683 K. As the temperature increased, the number of carbon atom at C3 per unit cell decreased, indicating the gradual removal of methyl groups. Measurement of the 6-ring aperture size revealed that heat-treated crystals had larger aperture sizes compared to untreated crystal 1. However, at 753 K, single-crystal X-ray diffraction data could not be obtained due to the loss of Co-ZIF-67 crystallinity. In the case of Co/Zn-ZIF-67 single crystals synthesized with different molar ratios, the structures were similar to those of Co-ZIF-67 single crystals, with Co exhibiting higher occupancy rates compare to Zn. Additionally, the Co/Zn-ZIF-67 demonstrated smaller unit cell parameters compared to Co-ZIF-67 (crystal 1). Consequently, the aperture size of the Co/Zn-ZIF-67 with tuning of the amount of Co and Zn was smaller than that of Co-ZIF-67 (crystal 1).\u003c/p\u003e","manuscriptTitle":"Fine-Tuning the Aperture Size of Co-ZIF-67 via Dehydration, Demethylation, and Co-Zn Hybridization","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-09-23 07:10:33","doi":"10.21203/rs.3.rs-7579437/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2025-10-12T16:49:22+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-10-11T09:28:54+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-26T13:13:21+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"7744215084867953990492791391868072426","date":"2025-09-19T12:52:14+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"191196356397027709558733378909688729218","date":"2025-09-15T13:03:27+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2025-09-14T17:40:50+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"116160278062483862879254254789745075409","date":"2025-09-14T13:02:51+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"170545213554454792865273008568302328671","date":"2025-09-14T12:42:29+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2025-09-14T12:35:21+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-09-11T06:36:57+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-09-11T06:36:32+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Porous Materials","date":"2025-09-10T06:30:10+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-porous-materials","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jopo","sideBox":"Learn more about [Journal of Porous Materials](http://link.springer.com/journal/10934)","snPcode":"10934","submissionUrl":"https://submission.nature.com/new-submission/10934/3","title":"Journal of Porous Materials","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"8ac56223-88f2-4611-bc06-7f2236a16be3","owner":[],"postedDate":"September 23rd, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-11-24T16:02:06+00:00","versionOfRecord":{"articleIdentity":"rs-7579437","link":"https://doi.org/10.1007/s10934-025-01882-y","journal":{"identity":"journal-of-porous-materials","isVorOnly":false,"title":"Journal of Porous Materials"},"publishedOn":"2025-11-19 15:58:00","publishedOnDateReadable":"November 19th, 2025"},"versionCreatedAt":"2025-09-23 07:10:33","video":"","vorDoi":"10.1007/s10934-025-01882-y","vorDoiUrl":"https://doi.org/10.1007/s10934-025-01882-y","workflowStages":[]},"version":"v1","identity":"rs-7579437","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-7579437","identity":"rs-7579437","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}