From zero-dimensional complexes to two-dimensional coordination polymers adjusted by metal ions or ligand substituent groups

From zero-dimensional complexes to two-dimensional coordination polymers adjusted by metal ions or ligand substituent groups | 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 From zero-dimensional complexes to two-dimensional coordination polymers adjusted by metal ions or ligand substituent groups Yong-Hong Zhou, Long-Feng Li, Yun Xu This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8392230/v1 This work is licensed under a CC BY 4.0 License Status: Under Review Version 1 posted 11 You are reading this latest preprint version Abstract Six novel Zn(II), Cd(II) and Co(II) mixed-ligand coordination complexes, namely, Cd(HOBA) 2 (DPE) 2 (H 2 O) 2 ( 1 ), Co(HOBA) 2 (DPE) 2 (H 2 O) 2 ( 2 ), [Zn(DPA) 2 (DPE)] n ( 3 ), [Zn(CPA) 2 (BPP)] n ( 4 ), [Cd 2 (CPA) 4 (BPP) 2 (H 2 O)] n ( 5 ), and [Cd(DPA) 2 (DPE)] n ( 6 ) (H 2 OBA = 4-carboxylphenoxyacetic acid, HDPA = 2,4-dichlorophenoxyacetic acid, HCPA = 2-chlorophenoxyacetic acid, DPE = 1,2-di(pyridin-4-yl)ethylene, BPP = 1,3-bis(4-pyridyl)propane) have been synthesized hydrothermally by the self-assembly of R-phenoxyacetic acid (R = 2,4-dichloro, 2-chloro and 4-carboxyl), N-donor ligands and Zn(II), Cd(II) or Co(II) salts. Single crystal X-ray analyses reveal that in complexes 1 and 2 , the H 2 OBA and DPE act as terminal ligands, generating 0D Cd(II) and Co(II) mononuclear molecules. Complexes 3 and 4 both show 1D chain structures, where the four-coordinated Zn(II) ions are bridged by DPE and BPP, respectively. For complex 5 , the six- and seven-coordinated Cd(II) ions are interconnected through carboxyl groups to form [Cd 2 (CPA) 4 ] building units, which are subsequently extended by BPP ligands into 1D chains. In complex 6 , adjacent Cd(II) ions are bridged by DPA − anions to form a 1D linear chain. Through the bridging of DPE ligands, the 1D chains undergo dimensional expansion and eventually evolve into 2D supramolecular architectures. Furthermore, the thermal stabilities and fluorescence properties of these complexes have also been investigated. Crystal structure Coordination polymer Zinc(II) complex Cobalt(II) complex Cadmium(II) complex Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Introduction Recent years have witnessed the growing interest of metal carboxylate complexes in supramolecular chemistry and material chemistry [ 1 – 2 ]. The motivation in this area arises from not only their promising applications in optics, biology, catalysis and adsorption, but also their fascinating structural multiplicities of architectures [ 3 – 5 ]. The carboxylate ligands can bind to metal atoms in monodentate, bidentate, bridging and chelating fashions, giving the formation of diverse structural motifs ranging from 0D molecules, 1D chains, 2D layers to 3D networks through coordination bond and/or weak interactions such as hydrogen bonding and π⋅⋅⋅π stacking interactions [ 6 – 7 ]. Compared to other synthetic parameters such as reaction temperature, pH, and solvent, ligand design remains the critical determinant of both topology and functionality of the final products. Hence, organic ligands with different length, sharp, rigidity and functional groups have been investigated to illustrate their roles in the construction of novel metal carboxylate complexes. Particularly, the coordination nature of the organic ligands can be relatively easily regulated by the incorporation of either electron-donating or electron-withdrawing substituents. The structural and electronic variations stemmed from the functionalization of the organic molecules can adjust the metal coordination sphere, thereby resulting in significant changes in the structural topology and physicochemical properties of the desired coordination complexes [ 8 – 16 ]. Li et al. have demonstrated that the modification of the 3-position substituent of imidazo[1,2- a ]pyridine from pyridine group to carboxylate group markedly influences the architecture and properties of the coordination complexes. Reactions of differently substituted imidazo[1,2-a]pyridine ligands with Zn(II) salts yielded 0D and 2D polymeric networks, respectively [ 17 ]. Our research also reveals that rational ligand engineering through substituent effects allows systematic modulation of coordination geometry and supramolecular packing. For example, the -SO 3 H and -OH substitution groups may act as H-bonding donor or acceptor, while the -NO 2 group shows remarkable spatial effect on the construction of novel supramolecular networks [ 18 ]. Recently, we focused on the construction of new metal-carboxylate system based on flexible/rigid carboxylate acids with the N-donor molecules as co-ligands [ 19 – 21 ]. As an extension of our effort in this field, and to further understand effects of organic ligands with different substitution groups and metal ions on the formation of resultant architectures, we selected HDPA, HCPA and H 2 OBA to react with Cd(II)/Zn(II)/Co(II) salts with the aids of DPE and BPP under hydrothermal conditions. Fortunately, six novel metal-carboxylate complexes, namely, Cd(HOBA) 2 (DPE) 2 (H 2 O) 2 ( 1 ), Co(HOBA) 2 (DPE) 2 (H 2 O) 2 ( 2 ), [Zn(DPA) 2 (DPE)] n ( 3 ), [Zn(CPA) 2 (BPP)] n ( 4 ), [Cd 2 (CPA) 4 (BPP) 2 (H 2 O)] n ( 5 ), and [Cd(DPA) 2 (DPE)] n ( 6 ) have been isolated. Herein, we present the crystal structures of these complexes, along with the systematic investigation of the substituent effect of the ligands and metal ions on the ultimate framework. Experimental section Materials and Physical Measurements All the reagents and solvents were of analytical grade and used as received without further purification. Elemental analysis was performed on a Vario EL III analyzer. The FT-IR spectra were measured on a Nicolet 510 FT-IR spectrophotometer with the KBr pellets in the range 4000 − 400 cm − 1 . Thermogravimetric analyses were done under nitrogen with a heating rate of 10°C min − 1 using a Shimadzu DTG-60H analyzer. The solid state luminescence spectra for the samples were obtained at room temperature with a RF-5301PC fluorescence spectrometer. Synthesis of Cd(HOBA) 2 (DPE) 2 (H 2 O) 2 (1). Cadmium acetate (0.0231 g, 0.1 mmol), H 2 OBA (0.0196 g, 0.1 mmol) and DPE (0.0182 g, 0.1 mmol) were dissolved in 10 mL distilled water. The resultant mixture was stirred for 30 min and then transferred to a Teflon-lined stainless steel vessel (20 mL). The vessel was sealed and heated at 140°C for 4 d, followed by cooling to room temperature naturally. Yellow crystals of 1 were collected in yield: 56%. Elemental analysis (%): Calcd. for C 42 H 38 N 4 O 12 Cd: C 55.80, H 4.21, and N 6.20. Found: C 55.76, H 4.18, and N 6.23. FT-IR (KBr pellet, cm − 1 ): 3410(br), 1721(m), 1627(s), 1552(s), 1369(s), 1165(m), 960(w), 850(w), 753(m), 673(w), 607(m), 570(w). Synthesis of Co(HOBA) 2 (DPE) 2 (H 2 O) 2 (2). The synthesis of 2 was similar to that for 1 except that cadmium acetate was replaced by cobalt acetate. Dark red crystals of 2 were collected in yield: 59%. Elemental analysis (%): Calcd. for C 42 H 38 N 4 O 12 Co: C 59.32, H 4.47, and N 6.59. Found: C 59.35, H 4.50, and N 6.56. FT-IR (KBr pellet, cm − 1 ): 3413(br), 1719(m), 1630(s), 1555(s), 1372(s), 1168(m), 965(w), 853(w), 756(m), 675(w), 609(m), 571(w). Synthesis of [Zn(DPA) 2 (DPE)] n (3). The synthesis of 3 was similar to that for 1 except that cadmium acetate and H 2 OBA were replaced by zinc acetate and HDPA, respectively. Colorless crystals of 3 were collected in yield: 45%. Elemental analysis (%): Calcd. for C 28 H 20 N 2 O 6 Cl 4 Zn: C 48.86, H 2.91, and N 4.07. Found: C 48.83, H 2.89, and N 4.05. FT-IR (KBr pellet, cm − 1 ): 3410(w), 1658(vs), 1616(s), 1457(m), 1410(s), 1289(m), 839 (w), 739(m), 511( m). Synthesis of [Zn(CPA) 2 (BPP)] n (4). The synthesis of 4 was similar to that for 3 except that HCPA and BPP were used instead of HDPA and DPE, respectively. Colorless crystals of 4 were collected in yield: 32%. Elemental analysis (%): Calcd. For C 29 H 26 Cl 2 N 2 O 6 Zn: C 54.82, H 4.10, and N 4.41. Found: C 54.80, H 4.07, and N 4.38. FT-IR (KBr pellet, cm − 1 ): 3409(w), 1655(vs), 1620(s), 1449(m), 1412(s), 1293(m), 840 (w), 737(m), 512(m). Synthesis of [Cd 2 (CPA) 4 (BPP) 2 (H 2 O)] n (5). The synthesis of 5 was similar to that for 1 except that H 2 OBA and DPE were replaced by HCPA and BPP, respectively. Yellow crystals of 5 were collected in yield: 41%. Elemental analysis (%): Calcd. for C 58 H 54 N 4 O 13 Cl 4 Cd 2 : C 50.37, H 3.91, and N 4.05. Found: C 50.33, H 3.87, and N 4.07. FT-IR (KBr pellet, cm − 1 ): 3421(br), 1630(vs), 1557(vs), 1470(m), 1375(s), 1135(m), 957(w), 850(w), 607(m), 561(w). Synthesis of [Cd(DPA) 2 (DPE)] n (6). The synthesis of 6 was similar to that for 1 except that H 2 OBA was replaced by HDPA. Pale yellow crystals were collected in yield: 39%. Elemental analysis (%): Calcd. for C 28 H 20 N 2 O 6 Cl 4 Cd: C 45.74, H 2.72, and N 3.81. Found: C 45.71, H 2.75, and N 3.83. FT-IR (KBr pellet, cm − 1 ): 1629(vs), 1600(s), 1475(vs), 1412(m), 1285(s), 1103(m), 1074(m), 939(w), 722(m), 613(w). X-ray Single-Crystal Structure Determination The structures of complexes 1 – 6 were acquired by single crystal X-ray diffraction analysis. Crystallographic data of 1 – 6 were collected at room temperature on a Bruker Smart Apex-II CCD diffractometer equipped with graphite-monochromated MoK α radiation (λ = 0.71073 Å), using the ω scan technique. The six structures were solved by direct methods and refined anisotropically with SHELXTL software package applying the full-matrix least-squares procedures against the F 2 values Table 1 Crystal data and structure refinement details for complexes 1 – 6. Compound 1 2 3 4 5 6 Formula C 42 H 38 N 4 O 12 Cd C 42 H 38 N 4 O 12 Co C 28 H 20 N 2 O 6 Cl 4 Zn C 29 H 26 Cl 2 N 2 O 6 Zn C 58 H 54 N 4 O 13 Cl 4 Cd 2 C 28 H 20 N 2 O 6 Cl 4 Cd Formula weight 903.16 849.69 687.63 634.79 1381.65 734.66 Temperature (K) 298(2) 296(2) 296(2) 296(2) 296(2) 296(2) Crystal system monoclinic monoclinic monoclinic orthorhombic monoclinic monoclinic Space group P 2 1 /c P 2 1 /c P 2 1 /c P 2 1 2 1 2 1 P 2 1 P2 1 /n Unit cell dimensions a (Å) 21.6675(17) 21.6218(11) 8.4164(8) 8.6433(9) 8.3574(9) 4.7878(6) b (Å) 5.8057(4) 5.7090(2) 20.7258(19) 13.0839(13) 13.0117(14) 13.2998(17) c (Å) 15.8638(13) 15.5937(8) 16.7137(15) 25.322(3) 26.714(3) 21.417(3) α (º) 90 90 90 90 90 90 β (º) 104.731(4) 103.484(2) 91.961(2) 90 92.042(2) 96.035(2) γ (º) 90 90 90 90 90 90 Volume/ Å 3 1930.0(3) 1871.81(15) 2913.8(5) 2863.6(5) 2903.1(6) 1356.2(3) Z 2 2 4 4 2 2 Density (calculated) (mg/mm 3 ) 1.554 1.508 1.568 1.472 1.581 1.799 Absorption coefficient (mm − 1 ) 0.638 0.533 1.255 1.090 0.983 1.248 θ range for data collection/(º) 1.944 to 25.242 1.937 to 25.242 1.944 to 25.242 2.825 to 22.799 2.439 to 25.000 3.063 to 24.990 F (000) 924 882 1392 1304 1396 732 Limiting indices -28 ≤ h ≤ 28, -7 ≤ k ≤ 7, -21 ≤ l ≤ 21 -28 ≤ h ≤ 27, -7 ≤ k ≤ 7, -20 ≤ l ≤20 -10 ≤ h ≤ 10, -27 ≤ k ≤ 25, -15 ≤ l ≤ 21 -11 ≤ h ≤ 10, -17 ≤ k ≤ 15, -28 ≤ l ≤ 31 -9 ≤ h ≤ 6, -15 ≤ k ≤ 15, -31 ≤ l ≤ 31 -5 ≤ h ≤ 5, -15 ≤ k ≤ 15, -25 ≤ l ≤ 21 Goodness-of-fit on F 2 1.068 1.046 1.005 0.952 0.893 1.035 Final R indices [ I > 2σ(I) ] R 1 = 0.0216, wR 2 = 0.0564 R 1 = 0.0379, wR 2 = 0.0915 R 1 = 0.0443, wR 2 = 0.0804 R 1 = 0.0382, wR 2 = 0.0716 R 1 = 0.0397, wR 2 = 0.0770 R 1 = 0.0224, wR 2 = 0.0510 Table 2 Selected bond lengths (Å) and bond angles (º) for complexes 1 – 6 [a] . Complex 1 Cd1-O5 2.2732(10) Cd1-O5A 2.2732(10) Cd1-O6 2.3064(10) Cd1-O6A 2.3064(10) Cd1-N1 2.3554(12) Cd1-N1A 2.3554(12) O5-Cd1-O5A 180.0 O5-Cd1-O6 92.15(4) O5-Cd1-O6A 87.85(4) O5-Cd1-O6A 87.85(4) O5A-Cd1-O6A 92.15(4) O5-Cd1-N1 91.87(4) O5-Cd1-N1A 88.13(4) O5A-Cd1-N1A 91.87(4) O5A-Cd1-N1 88.13(4) O6-Cd1-O6A 180.0 O6-Cd1-N1 84.94(4) O6A-Cd1-N1 84.94(4) O6A-Cd1-N1 95.06(4) O6-Cd1-N1A 95.06(4) N1-Cd1-N1A 180.00(6) Complex 2 Co1-O1 2.0936(11) Co1-O1A 2.0936(11) Co1-O6 2.1034(12) Co1-O6A 2.1034(12) Co1-N2 2.1763(14) Co1-N2A 2.1763(14) O1-Co1-O1A 180.00(5) O1-Co1-O6 87.29(5) O1-Co1-O6A 92.70(5) O1A-Co1-O6 92.71(5) O1A-Co1-O6A 87.30(5) O1-Co1-N2 90.71(5) O1-Co1-N2A 89.29(5) O1A-Co1-N2 90.71(5) O1A-Co1-N2 89.29(5) O6-Co1-O6A 180.0 O6-Co1-N2 94.49(5) O6-Co1-N2A 94.49(5) O6A-Co1-N2 85.51(5) O6-Co1-N2A 85.51(5) N2-Co1-N2A 180.0 Complex 3 Zn1-O3 1.9563(18) Zn1-O4 1.9584(19) Zn1-N1 2.028(2) Zn1-N2 2.022(2) O3-Zn1-O4 95.14(8) O3-Zn1-N1 110.85(9) O3-Zn1-N2 110.06(9) O4-Zn1-N1 115.22(9) O4-Zn1-N2 108.45(9) N2-Zn1-N1 115.29(9) Complex 4 Zn1-N2 2.053(3) Zn1-O4 1.945(3) Zn1-N1 2.031(3) Zn1-O3 1.936(3) O4-Zn1-N2 96.04(12) O4-Zn1-N1 106.07(13) N1-Zn1-N2 112.96(12) O3-Zn1-N2 104.86(13) O3-Zn1-O4 115.00(13) O3-Zn1-N1 119.55(14) Complex 5 Cd1-O2 2.323(6) Cd1-N1 2.345(6) Cd1-N2 2.347(6) Cd1-O5 2.360(5) Cd1-O8 2.383(5) Cd1-O4 2.538(6) Cd1-O3 2.590(6) Cd2-O7 2.216(5) Cd2-N4 2.302(6) Cd2-N3 2.322(6) Cd2-O13 2.331(5) Cd2-O11 2.391(6) Cd2-O10 2.402(6) O2-Cd1-N1 135.4(2) O2-Cd1-N2 96.8(2) N1-Cd1-N2 94.4(2) O2-Cd1-O5 137.0(2) N1-Cd1-O5 83.6(2) N2-Cd1-O5 97.1(2) O2-Cd1-O8 77.7(2) N1-Cd1-O8 89.8(2) N2-Cd1-O8 174.5(2) O5-Cd1-O8 87.0(2) O2-Cd1-O4 88.2(2) N1-Cd1-O4 135.8(2) N2-Cd1-O4 85.3(2) O5-Cd1-O4 52.80(19) O8-Cd1-O4 94.20(19) O2-Cd1-O3 52.7(2) N1-Cd1-O3 85.6(2) N2-Cd1-O3 85.5(2) O5-Cd1-O3 169.0(2) O8-Cd1-O3 91.25(19) O4-Cd1-O3 138.14(19) O7-Cd2-N4 126.8(2) O7-Cd2-N3 86.8(2) N4-Cd2-N3 100.0(2) O7-Cd2-O13 84.6(2) N4-Cd2-O13 84.8(2) N3-Cd2-O13 171.4(2) O7-Cd2-O11 149.5(2) N4-Cd2-O11 83.7(2) N3-Cd2-O11 88.7(2) O13-Cd2-O11 99.0(2) O7-Cd2-O10 95.3(2) N4-Cd2-O10 136.3(2) N3-Cd2-O10 92.6(2) O13-Cd2-O10 88.8(2) O11-Cd2-O10 54.76(19) Complex 6 Cd1-O3 2.3066(15) Cd1-O3A 2.3066(15) Cd1-O2 2.3188(15) Cd1-O2A 2.3188(15) Cd1-N1 2.3707(18) Cd1-N1A 2.3707(18) O3-Cd1-O3A 180.0 O3-Cd1-O2 94.31(5) O3-Cd1-O2A 85.69(5) O3A-Cd1-O2 85.69(5) O3A-Cd1-O2A 94.31(5) O2-Cd1-O2A 180.0 O3-Cd1-N1 85.15(6) O3-Cd1-N1A 94.85(6) O2-Cd1-N1 92.21(6) O2-Cd1-N1A 87.79(6) O3A-Cd1-N1 94.85(6) O3A-Cd1-N1A 85.15(6) O2A-Cd1-N1 87.79(6) O2A-Cd1-N1A 92.21(6) N1-Cd1-N1A 180.0 [a] Symmetry Code: Complex 1 : -x, y + 1/2, -z + 1/2; Complex 2 : -x, y + 1/2, -z + 1/2; Complex 6 : -x, -y, -z. [ 22 ]. All non-hydrogen atoms were refined based on their anisotropic thermal parameters. The hydrogen atoms were located at calculated distances and refined by fixed isotropic thermal parameters as riding atoms. The crystallographic data for 1–6 are presented in Table 1 , selected bond lengths and angles for 1 – 6 are listed in Table 2 . Results and discussion Structures of 1 and 2. Single crystal X-ray diffraction analysis shows that complexes 1 and 2 are isomorphous, belonging to monoclinic crystal system with space group P 2 1 /c, hence, only the structure of complex 1 is described in detail. There are a half Cd(II) atom, one HOBA − ligand, one DPE ligand and one coordinated water molecule in the asymmetric unit. As shown in Fig. 1 a, in the molecular structure of 1 , two oxygen atoms from two individual HOBA − ligands, two coordinated water molecules and two nitrogen atoms from two DPE ligands complete the coordination environment of Cd(II) ion, which shows a distorted octahedron geometry. The Cd-N bond length is 2.3554(12) Å, and the Cd-O distances are 2.2732(10) and 2.3064(10) Å, respectively. H 2 OBA bears one flexible carboxyl group and one rigid carboxyl group, and this often gives rise to the formation of high-dimensional products [ 23 – 24 ]. However, in compound 1 , H 2 OBA is partly deprotonated and only the flexible carboxyl group is bound to the central atoms in monodentate fashion. In addition, the DPE ligands in 1 display monodentate mode. The above mentioned factors lead to the formation of zero-dimensional complex of 1 . Furthermore, the mononuclear molecules are linked by intermolecular C-H⋅⋅⋅O hydrogen bonds between the phenyl ring and carboxyl group into a 2D network (Fig. 1 b). The coordination mode observed in complex 1 is very different from that in other compounds. For example, in{[Cd 2 (OBA) 2 (BIB) 2 ](H 2 O) 7 } n (BIB = 1,4-bis(imidazol-1-yl)-butane)) [ 23 ] and [Cd(OBA)(H 2 O) 3 ] n [ 24 ], both the rigid and flexible carboxyl groups adopt bidentate-bridging mode, linking central ions to generate 1D chain. Figure 1 a Coordination environment of Cd(II) ions in complex 1 , all the hydrogen atoms have been deleted for clarity. Structure of 3. Complex 3 crystallizes in monoclinic P 2 1 /c space group. The asymmetric unit of 3 consists of a half Zn(II) atom, one DPA − and a half DPE ligand. The central Zn(II) atom has a slightly distorted tetrahedral arrangement and is surrounded by two oxygen atoms from two DPA − anions, and two nitrogen atoms from different DPE molecules (Fig. 2 a). The Zn-O bond lengths are 1.9563(18) and 1.9584(19) Å, and the Zn-N distances are 2.028(2) and 2.022(2) Å, respectively. The pyridine rings of the DPE molecule are twisted slightly to each other as indexed by the dihedral angle of 13.3°. Each DPE links two Zn(II) atoms to form an infinite 1D chain with the Zn⋅⋅⋅Zn distance of 13.3022(8) Å (Fig. 2 b). The DPA − ligands adopt monodentate mode, decorating the 1D chain on both sides. The 1D chains are further extended into a 2D plane through C-H⋅⋅⋅O and and C-H⋅⋅⋅Cl hydrogen bonding interactions (Fig. 2 c). Figure 2 a Coordination environment of Zn(II) ions in complex 3 , all of the hydrogen atoms have been deleted for clarity. Figure 2 b View of the 1D chain in complex 3 , all the hydrogen atoms have been deleted for clarity. Structure of 4. Complex 4 crystallizes in orthorhombic P2 1 2 1 2 1 space group. As depicted in Fig. 3 a, the Zn(II) atom is tetra-coordinated by two oxygen atoms of two individual CPA − ligands and two nitrogen atoms from two BPP molecules in a tetrahedron coordination environment (Fig. 3 a). The Zn-O distances fall into 1.936(3)-1.945(3) Å, and Zn-N bond lengths are 2.031(3)-2.053(3) Å. These data are comparable to those observed in related Zn-O/N coordination polymers [ 25 – 27 ]. The BPP ligands assume cis- conformation, bridging adjacent Zn(II) atoms to form 1D chain along the b axis with the Zn⋅⋅⋅Zn separation of 13.0839(13) Å (Fig. 3 b). The neighboring chains are further linked through intermolecular C-H⋅⋅⋅O interactions between the phenyl ring and carboxyl groups to afford the final 2D supramolecular architecture (Fig. 3 c). Figure 3 a Coordination environment of Zn(II) ions in complex 4 , all of the hydrogen atoms have been deleted for clarity. Figure 3 b View of the 1D chain in complex 4 along b direction, all of the hydrogen atoms have been deleted for clarity. Structure of complex 5. Complex 5 crystallizes in monoclinic system with space group P2 1 . There exist two crystallographically independent Cd(II) atoms bearing two different coordination geometries in the asymmetric unit. As illustrated in Fig. 4 a, Cd1 ion lies in a distorted pentagonal-bipyramidal coordination sphere, which is defined by five oxygen atoms from three CPA − ligands, and two nitrogen atoms from two BPP molecules. The equatorial plane contains four oxygen atoms (Cd1-O2 = 2.323(6), Cd1-O3 = 2.590(6), Cd1-O4 = 2.538(6) and Cd1-O5 = 2.360(5) Å) originating from three CPA − , and one nitrogen atom from one BPP ligand (Cd1-N1 = 2.345(6) Å ); one nitrogen atom of BPP and one oxygen atom of CPA − (Cd1-N2 = 2.347(6) and Cd1-O8 = 2.383(5) Å ) locate at the remaining axial positions. Cd2 center lies in a distorted octahedral coordination sphere formed by three oxygen atoms from two CPA − ligands, two nitrogen atoms of two BPP ligands and one coordinated water molecule. The O7, O10, O11 and N4 atoms fulfill the equatorial plane (Cd1-O7 = 2.216(5), Cd1-O10 = 2.402(6), Cd1-O11 = 2.391(6) and Cd1-N4 = 2.302(6) Å); and the N3 and O13 atoms occupy the axial positions (Cd1-N3 = 2.322(6) and Cd1-O13 = 2.331(5) Å). The deprotonated CPA − ligands exhibit chelating and syn-anti bidentate bridging coordination modes; hence, a pair of Cd(II) atoms are connected to form [Cd 2 O 2 ] unit with the Cd⋅⋅⋅Cd separation of 5.4307(4) Å. Frequently, the dinuclear cadmium unit can be formed by µ -acetato-O,O′, monoatomic and µ -H 2 O bridges and different bridging modes often result in different Cd⋅⋅⋅Cd distances. For example, the Cd⋅⋅⋅Cd distance (5.4307(4) Å) in 5 is significant longer than that found for the µ -H 2 O bridged [Cd 2 (bpy) 2 (OAc) 4 (H 2 O) 2 ] (3.6889(9) Å) [ 28 ] and cadmium-tetracarboxylate complex [Cd 2 (4,4'-bipy)(3,3'-bpda) 2 ] n (3,3'-bpda = 1,1'-biphenyl-3,3'-dicarboxylate, 4,4'-bipy = 4,4'-bipyridine) (3.050(1) Å) [ 29 ], but much shorter than that observed in the bis-monoatomic bridged [Cd(pydc)(phen)] n (H 2 pydc = pyridine-2,3-dicarboxylic acid) (6.252(4) Å) [ 30 ]. Furthermore, along the b axis, the [Cd 2 O 2 ] units are connected by the BPP ligands to give the formation of 1D double chain with the Cd⋅⋅⋅Cd separation of 13.0117(14) Å (Fig. 4 b). Cd(II) complexes based on phenoxyacetic acid derivatives and BPP ligands have been previously reported. For example, in [Cd 4 (DPA) 8 (BPP) 4 (H 2 O) 2 ] n , the HDPA shows bidentate bridging and monoatomic bridging fashions [ 21 ]. These differences imply that the substituent group plays an important role in directing the final structure. Structure of complex 6. X-ray analysis of complex 6 reveals that it crystallizes in monoclinic space group P2 1 /n. The asymmetric unit contains one Cd(II) atom, one DPA − ligand and a half DPE molecule. As shown in Fig. 5 a, each Cd(II) center is six-coordinated in a distorted octahedral geometry, which is defined by four oxygen atoms from four DPA − ligands, and two nitrogen atoms from two DPE ligands. The equatorial plane is composed of four oxygen atoms originating from four bridging DPA − anions; two nitrogen atoms of two DPE occupy the remaining axial positions. The Cd-N bond lengths are 2.3707(18) Å and the Cd-O ones are in the range of 2.3066(15) − 2.3188(15) Å, respectively. In addition, the coordination angles around Cd ion span from 85.15(6) to 180.0 º. These structure parameters are in the normal range for similar Cd-O/ N systems [ 31 – 35 ]. DPA − anions adopting syn-anti bidentate bridging coordination mode, link neighboring Cd(II) atoms to form [Cd 2 O 4 ] unit with the Cd⋅⋅⋅Cd separation of 4.7878(6) Å. It is interesting to note that the Cd⋅⋅⋅Cd value in 5 is longer than that observed in 6 , the difference may arise from that the Cd(II) atoms in 6 are bridged by two carboxyl groups, while in 5 , only one carboxyl group acts as bridge between the two Cd(II) atoms. The dinuclear cadmium units are linked by DPA − ligands to form one-dimensional chain along a direction (Fig. 5 b). Furthermore, The exo-bidentate DPE may be regarded as a pillar of the [Cd 2 (DPA) 4 ] n chain through trans coordinating to the [Cd 2 O 4 ] units of different chains along the direction of the b- axis with the Cd⋅⋅⋅Cd separation of 14.1353(16) Å, resulting the formation of 2D layer (Fig. 5 c). Structural comparison of complexes 1–6. The structural differences of complexes 1 – 6 indicate the role of central atoms and ligands with different substituent groups in fabricating metal-organic compounds (Table 3 ). Though zinc and cadmium fall into the identical periodic group, they show different coordination natures. In complexes 3 and 4 , the Zn(II) atoms are tetra-coordinated with two oxygen atoms and two nitrogen atoms. The carboxyl groups of DPA − and CPA − ligands exhibits monodentate fashion in both complexes. However, in 1 , 5 and 6 , the Cd(II) atoms are hexa- or hepta-coordinated by oxygen and nitrogen atoms from the carboxylate acids, N-donor ligands and coordinated water molecules. On the other hand, the difference between HDPA and HCPA lies in that HDPA has an additional chlorine atom at the 4-position compared to HCPA, and this distinction has a subtle effect on the coordination mode of carboxyl groups. Though HDPA and HCPA share the same coordination fashion in complexes 3 and 4 , they exhibit different coordination modes in complexes 5 and 6 . In complex 5 , the CPA − ligand shows bidentate bridging and chelating fashion, bridging hexa- or hepta-coordinated Cd(II) atoms to generate 1D double chain. However, the DPA − ligand in complex 6 assumes bidentate bridging mode, linking adjacent Cd(II) ions to form 1D chain. The effect of substituent on structures can also be found in complexes 1 and 6 . The H 2 OBA ligand simultaneously bears flexible and rigid carboxyl groups, with multiple coordination sites, which facilitate the formation of high-dimensional coordination complexes. However, the rigid carboxyl group does not participate in coordination, and the flexible carboxyl group adopts monodentate mode in complex 1 . Moreover, the DPE ligands coordinate to the central atoms in monodentate mode, which differs from that observed in 3 and 6 . These factors hinder the formation of high dimensional network, leading to 0D mononuclear structure of 1 . The present results further illustrate that central atoms and organic ligands with different substituent groups have significant influence on the final structures of the complexes. Thermogravimetric analysis Thermogravimetric (TG) measurements of crystalline compounds 1 – 6 were carried out in a nitrogen atmosphere from 20 to 700°C (Fig. 6 ). For compound 1 , a moderate mass decline of 4.12% (calculated 3.99%) was noted between 110 and 150°C, attributed to the loss of two coordinated water molecules. The dehydrated complex started to decompose above 230°C, ultimately yielding CdO (observed 13.91%; calculated 14.22%) as the residue. Compound 2 released one coordinated water molecule between 100 and 150°C, with an observed mass loss of 4.05% (calculated 4.24%). A subsequent rapid mass decrease related to organic ligand decomposition began at 235°C, with the process finally giving CoO (observed 8.52%; calculated 8.82%) as the end product. Only one major mass loss was detected for complexes 3 , 4 , and 6 . These materials remained stable up to approximately 220°C, after which substantial decomposition took place, corresponding to the elimination of their organic components. The residual masses matched well with the formation of ZnO (observed 11.93%; calculated 11.84%) for 3 , ZnO (observed 11.90%; calculated 12.82%) for 4 and CdO (observed 17.98%; calculated 17.48%) for 6 . In the case of compound 5 , a minor mass reduction of 1.35% (calculated 1.30%) occurred between 120 and 160°C, associated with the removal of one coordinated water molecule. The resulting dehydrated solid remained stable until 270°C, beyond which ligand decomposition occurred, leaving CdO (observed 18.51%; calculated 18.59%) as the final product. Table 3 Structural comparison for complexes 1 – 6. Compound Central atom Carboxylate ligand Coordination polyhedron Coordination fashion of the carboxyl group dimensionality Secondary interaction 1 Cd 2+ 4-carboxylphenoxyacetic acid (H 2 OBA) octahedron monodentate 0D H-bonding 2 Co 2+ 4-carboxylphenoxyacetic acid (H 2 OBA) octahedron monodentate 0D H-bonding 3 Zn 2+ 2,4-dichlorophenoxyacetic acid (HDPA) tetrahedron monodentate 1D linear chain H-bonding 4 Zn 2+ 2-chlorophenoxyacetic acid (HCPA) tetrahedron monodentate 1D linear chain H-bonding 5 Cd 2+ 2-chlorophenoxyacetic acid (HCPA) octahedron, pentagonal bipyramid chelating, bidentate bridging 1D double chain 6 Cd 2+ 2,4-dichlorophenoxyacetic acid (HDPA) octahedron bidentate bridging 2D layer Photoluminescence properties Coordination polymers with d 10 closed-shell electronic configuration metal ions can incorporate ligands with specific fluorescent properties, and their rigid frameworks can reduce non-radiative relaxation, thereby enhancing fluorescence emission. As a result, coordination polymers are regarded as a class of promising luminescent materials. Moreover, the synergistic functionalization of permanent porosity and luminescent properties endows coordination polymers with significant potential for applications in fluorescence. As previously reported, the free ligands BPP and DPE show fluorescence in the solid state, with emission peaks observed at 468 nm and 530 nm, respectively [ 18 , 36 – 37 ]. These emissions can be assigned to π* → π or π* → n electronic transitions [ 38 – 39 ]. As shown in Fig. 7 , compounds 3 – 6 exhibit distinct fluorescent emission bands: 470 nm (λex = 285 nm) for 3 , 445 nm (λex = 330 nm) for 4 , 441 nm (λex = 330 nm) for 5 , and 465 nm (λex = 285 nm) for 6 . Compared with the emissions of the free ligands, complexes 3 – 6 show blue shifts of approximately 60 nm, 23 nm, 27 nm and 65 nm, respectively. In compounds containing Zn(II) or Cd(II) ions with d¹⁰ configuration, emission typically does not originate from metal-to-ligand charge transfer (MLCT) or ligand-to-metal charge transfer (LMCT), since d¹⁰ metal ions are generally neither easily oxidized nor reduced [ 40 – 42 ]. Therefore, the emission of 3 – 6 is likely attributed to intraligand charge transfer. The observed blue shifts and variations in emission intensity among these complexes are probably due to differences in the coordination modes of the aromatic carboxylate ligands and the distinct coordination environments of the metal centers [ 43 ]. Conclusions Six Zn(II)/Cd(II) and Co(II) complexes have been constructed using R-phenoxyacetic acids and auxiliary N-donor ligands under hydrothermal conditions. Although these compounds are obtained under similar synthetic conditions, the different coordination fashions of the carboxylic acids and N-donor ligands result in various molecular architectures ranging from 0D mononuclear molecule, 1D chain to 2D layer. The structural diversity between these complexes indicates that organic ligands with different substituent groups and central metals play important roles in the construction of complexes. In addition, the hydrogen bond interactions are conducive to the formation of supramolecular structure. These results may give us some inspiration in the controllable preparation of desired coordination polymers tailed with specific functions and structures. Declarations Conflict of interest The authors declare no competing interests. Funding This work was supported by Scientific Research Foundation of Anhui Provincial Education Department (KJ2019A0597 and KJ2020A0022). Author Contribution Study conception and experimental design were by Yonghong Zhou and Longfeng Li. Experimental work, data collection and analyses were by Yonghong Zhou and Yun Xu. The original draft was prepared by Yonghong Zhou. All authors took part in revising the manuscript, and all have read and approved the final draft. Data Availability CCDC 2503460-2502465 for **1** - **6** contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via the internet at http://www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing [ [email protected] ](mailto: [email protected] ) . References Yuan F, Du YT, Shen SS, Hu HM, Zhou CS, Qiao CF, Cao BY, Singh A, Kumar A (2025) Luminescent properties and hirshfeld surface analyses of two new 3D Zn(II) coordination polymers assembled from isomeric terpyridyl carboxylate derivative and terephthalate ligands. 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Cite Share Download PDF Status: Under Review Version 1 posted Editorial decision: Revision requested 06 Mar, 2026 Reviews received at journal 27 Feb, 2026 Reviews received at journal 23 Feb, 2026 Reviewers agreed at journal 12 Feb, 2026 Reviewers agreed at journal 11 Feb, 2026 Reviews received at journal 09 Feb, 2026 Reviewers agreed at journal 31 Jan, 2026 Reviewers invited by journal 30 Jan, 2026 Editor assigned by journal 19 Dec, 2025 Submission checks completed at journal 19 Dec, 2025 First submitted to journal 18 Dec, 2025 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8392230","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":583540284,"identity":"ab6674f3-52a3-42e3-803c-37ed0c928ecb","order_by":0,"name":"Yong-Hong 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clarity.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-8392230/v1/ddab59427afb33c4d08f4e53.png"},{"id":101729937,"identity":"b8bc46de-8b58-4ab2-bbcc-729a296ba5d0","added_by":"auto","created_at":"2026-02-03 05:49:22","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":182938,"visible":true,"origin":"","legend":"\u003cp\u003ea Coordination environment of Cd(II) ions in complex \u003cstrong\u003e6\u003c/strong\u003e, all the hydrogen atoms have been deleted for clarity.\u003c/p\u003e\n\u003cp\u003eb View of the 1D chain in \u003cstrong\u003e6\u003c/strong\u003ealong \u003cem\u003ea\u003c/em\u003e direction. All the hydrogen atoms are omitted and only N atoms of DPE are kept for clarity.\u003c/p\u003e\n\u003cp\u003ec View of the 2D layer along \u003cem\u003eab\u003c/em\u003eplane. All the hydrogen atoms are omitted and only the carboxyl groups of HDPA are kept for clarity.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-8392230/v1/2434a4264a594bf07a11053e.png"},{"id":101754126,"identity":"c6b3f073-49fe-4ce2-9f9e-1860cd0516d0","added_by":"auto","created_at":"2026-02-03 10:41:41","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":59851,"visible":true,"origin":"","legend":"\u003cp\u003eTG curves for complexes \u003cstrong\u003e1\u003c/strong\u003e-\u003cstrong\u003e6\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-8392230/v1/399e061f058a36adde5b3a40.png"},{"id":101754003,"identity":"2c924d44-0442-4980-ba84-64ce00a2d146","added_by":"auto","created_at":"2026-02-03 10:41:20","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":58965,"visible":true,"origin":"","legend":"\u003cp\u003eThe emission spectra of compounds \u003cstrong\u003e3\u003c/strong\u003e-\u003cstrong\u003e6\u003c/strong\u003e in the solid state at room temperature.\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-8392230/v1/99a480a50edd67bd26d9cf26.png"},{"id":101756805,"identity":"8338d6c7-d9bf-49c9-a965-d877f78768fd","added_by":"auto","created_at":"2026-02-03 11:00:29","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2021227,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8392230/v1/67a51b41-45f0-471f-af66-40cb8b631921.pdf"}],"financialInterests":"No competing interests reported.","formattedTitle":"From zero-dimensional complexes to two-dimensional coordination polymers adjusted by metal ions or ligand substituent groups","fulltext":[{"header":"Introduction","content":"\u003cp\u003eRecent years have witnessed the growing interest of metal carboxylate complexes in supramolecular chemistry and material chemistry [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. The motivation in this area arises from not only their promising applications in optics, biology, catalysis and adsorption, but also their fascinating structural multiplicities of architectures [\u003cspan additionalcitationids=\"CR4\" citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. The carboxylate ligands can bind to metal atoms in monodentate, bidentate, bridging and chelating fashions, giving the formation of diverse structural motifs ranging from 0D molecules, 1D chains, 2D layers to 3D networks through coordination bond and/or weak interactions such as hydrogen bonding and π\u0026sdot;\u0026sdot;\u0026sdot;π stacking interactions [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. Compared to other synthetic parameters such as reaction temperature, pH, and solvent, ligand design remains the critical determinant of both topology and functionality of the final products. Hence, organic ligands with different length, sharp, rigidity and functional groups have been investigated to illustrate their roles in the construction of novel metal carboxylate complexes. Particularly, the coordination nature of the organic ligands can be relatively easily regulated by the incorporation of either electron-donating or electron-withdrawing substituents. The structural and electronic variations stemmed from the functionalization of the organic molecules can adjust the metal coordination sphere, thereby resulting in significant changes in the structural topology and physicochemical properties of the desired coordination complexes [\u003cspan additionalcitationids=\"CR9 CR10 CR11 CR12 CR13 CR14 CR15\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. Li et al. have demonstrated that the modification of the 3-position substituent of imidazo[1,2-\u003cem\u003ea\u003c/em\u003e]pyridine from pyridine group to carboxylate group markedly influences the architecture and properties of the coordination complexes. Reactions of differently substituted imidazo[1,2-a]pyridine ligands with Zn(II) salts yielded 0D and 2D polymeric networks, respectively [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e]. Our research also reveals that rational ligand engineering through substituent effects allows systematic modulation of coordination geometry and supramolecular packing. For example, the -SO\u003csub\u003e3\u003c/sub\u003eH and -OH substitution groups may act as H-bonding donor or acceptor, while the -NO\u003csub\u003e2\u003c/sub\u003e group shows remarkable spatial effect on the construction of novel supramolecular networks [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eRecently, we focused on the construction of new metal-carboxylate system based on flexible/rigid carboxylate acids with the N-donor molecules as co-ligands [\u003cspan additionalcitationids=\"CR20\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. As an extension of our effort in this field, and to further understand effects of organic ligands with different substitution groups and metal ions on the formation of resultant architectures, we selected HDPA, HCPA and H\u003csub\u003e2\u003c/sub\u003eOBA to react with Cd(II)/Zn(II)/Co(II) salts with the aids of DPE and BPP under hydrothermal conditions. Fortunately, six novel metal-carboxylate complexes, namely, Cd(HOBA)\u003csub\u003e2\u003c/sub\u003e(DPE)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003e1\u003c/b\u003e), Co(HOBA)\u003csub\u003e2\u003c/sub\u003e(DPE)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003e2\u003c/b\u003e), [Zn(DPA)\u003csub\u003e2\u003c/sub\u003e(DPE)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e3\u003c/b\u003e), [Zn(CPA)\u003csub\u003e2\u003c/sub\u003e(BPP)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e4\u003c/b\u003e), [Cd\u003csub\u003e2\u003c/sub\u003e(CPA)\u003csub\u003e4\u003c/sub\u003e(BPP)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e5\u003c/b\u003e), and [Cd(DPA)\u003csub\u003e2\u003c/sub\u003e(DPE)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e6\u003c/b\u003e) have been isolated. Herein, we present the crystal structures of these complexes, along with the systematic investigation of the substituent effect of the ligands and metal ions on the ultimate framework.\u003c/p\u003e"},{"header":"Experimental section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials and Physical Measurements\u003c/h2\u003e \u003cp\u003eAll the reagents and solvents were of analytical grade and used as received without further purification. Elemental analysis was performed on a Vario EL III analyzer. The FT-IR spectra were measured on a Nicolet 510 FT-IR spectrophotometer with the KBr pellets in the range 4000\u0026thinsp;\u0026minus;\u0026thinsp;400 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e. Thermogravimetric analyses were done under nitrogen with a heating rate of 10\u0026deg;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e using a Shimadzu DTG-60H analyzer. The solid state luminescence spectra for the samples were obtained at room temperature with a RF-5301PC fluorescence spectrometer.\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of Cd(HOBA)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(DPE)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(1).\u003c/b\u003e\u003c/p\u003e \u003cp\u003eCadmium acetate (0.0231 g, 0.1 mmol), H\u003csub\u003e2\u003c/sub\u003eOBA (0.0196 g, 0.1 mmol) and DPE (0.0182 g, 0.1 mmol) were dissolved in 10 mL distilled water. The resultant mixture was stirred for 30 min and then transferred to a Teflon-lined stainless steel vessel (20 mL). The vessel was sealed and heated at 140\u0026deg;C for 4 d, followed by cooling to room temperature naturally. Yellow crystals of \u003cb\u003e1\u003c/b\u003e were collected in yield: 56%. Elemental analysis (%): Calcd. for C\u003csub\u003e42\u003c/sub\u003eH\u003csub\u003e38\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e12\u003c/sub\u003eCd: C 55.80, H 4.21, and N 6.20. Found: C 55.76, H 4.18, and N 6.23. FT-IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3410(br), 1721(m), 1627(s), 1552(s), 1369(s), 1165(m), 960(w), 850(w), 753(m), 673(w), 607(m), 570(w).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of Co(HOBA)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(DPE)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(2).\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe synthesis of \u003cb\u003e2\u003c/b\u003e was similar to that for \u003cb\u003e1\u003c/b\u003e except that cadmium acetate was replaced by cobalt acetate. Dark red crystals of \u003cb\u003e2\u003c/b\u003e were collected in yield: 59%. Elemental analysis (%): Calcd. for C\u003csub\u003e42\u003c/sub\u003eH\u003csub\u003e38\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e12\u003c/sub\u003eCo: C 59.32, H 4.47, and N 6.59. Found: C 59.35, H 4.50, and N 6.56. FT-IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3413(br), 1719(m), 1630(s), 1555(s), 1372(s), 1168(m), 965(w), 853(w), 756(m), 675(w), 609(m), 571(w).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of [Zn(DPA)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(DPE)]\u003c/b\u003e \u003csub\u003e \u003cb\u003en\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(3).\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe synthesis of \u003cb\u003e3\u003c/b\u003e was similar to that for \u003cb\u003e1\u003c/b\u003e except that cadmium acetate and H\u003csub\u003e2\u003c/sub\u003eOBA were replaced by zinc acetate and HDPA, respectively. Colorless crystals of \u003cb\u003e3\u003c/b\u003e were collected in yield: 45%. Elemental analysis (%): Calcd. for C\u003csub\u003e28\u003c/sub\u003eH\u003csub\u003e20\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eCl\u003csub\u003e4\u003c/sub\u003eZn: C 48.86, H 2.91, and N 4.07. Found: C 48.83, H 2.89, and N 4.05. FT-IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3410(w), 1658(vs), 1616(s), 1457(m), 1410(s), 1289(m), 839 (w), 739(m), 511( m).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of [Zn(CPA)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(BPP)]\u003c/b\u003e \u003csub\u003e \u003cb\u003en\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(4).\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe synthesis of \u003cb\u003e4\u003c/b\u003e was similar to that for \u003cb\u003e3\u003c/b\u003e except that HCPA and BPP were used instead of HDPA and DPE, respectively. Colorless crystals of \u003cb\u003e4\u003c/b\u003e were collected in yield: 32%. Elemental analysis (%): Calcd. For C\u003csub\u003e29\u003c/sub\u003eH\u003csub\u003e26\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eZn: C 54.82, H 4.10, and N 4.41. Found: C 54.80, H 4.07, and N 4.38. FT-IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3409(w), 1655(vs), 1620(s), 1449(m), 1412(s), 1293(m), 840 (w), 737(m), 512(m).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of [Cd\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(CPA)\u003c/b\u003e \u003csub\u003e \u003cb\u003e4\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(BPP)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(H\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003eO)]\u003c/b\u003e \u003csub\u003e \u003cb\u003en\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(5).\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe synthesis of \u003cb\u003e5\u003c/b\u003e was similar to that for \u003cb\u003e1\u003c/b\u003e except that H\u003csub\u003e2\u003c/sub\u003eOBA and DPE were replaced by HCPA and BPP, respectively. Yellow crystals of \u003cb\u003e5\u003c/b\u003e were collected in yield: 41%. Elemental analysis (%): Calcd. for C\u003csub\u003e58\u003c/sub\u003eH\u003csub\u003e54\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e13\u003c/sub\u003eCl\u003csub\u003e4\u003c/sub\u003eCd\u003csub\u003e2\u003c/sub\u003e: C 50.37, H 3.91, and N 4.05. Found: C 50.33, H 3.87, and N 4.07. FT-IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 3421(br), 1630(vs), 1557(vs), 1470(m), 1375(s), 1135(m), 957(w), 850(w), 607(m), 561(w).\u003c/p\u003e \u003cp\u003e \u003cb\u003eSynthesis of [Cd(DPA)\u003c/b\u003e \u003csub\u003e \u003cb\u003e2\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(DPE)]\u003c/b\u003e \u003csub\u003e \u003cb\u003en\u003c/b\u003e \u003c/sub\u003e \u003cb\u003e(6).\u003c/b\u003e\u003c/p\u003e \u003cp\u003eThe synthesis of \u003cb\u003e6\u003c/b\u003e was similar to that for \u003cb\u003e1\u003c/b\u003e except that H\u003csub\u003e2\u003c/sub\u003eOBA was replaced by HDPA. Pale yellow crystals were collected in yield: 39%. Elemental analysis (%): Calcd. for C\u003csub\u003e28\u003c/sub\u003eH\u003csub\u003e20\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eCl\u003csub\u003e4\u003c/sub\u003eCd: C 45.74, H 2.72, and N 3.81. Found: C 45.71, H 2.75, and N 3.83. FT-IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e): 1629(vs), 1600(s), 1475(vs), 1412(m), 1285(s), 1103(m), 1074(m), 939(w), 722(m), 613(w).\u003c/p\u003e \u003c/div\u003e\n\u003ch3\u003eX-ray Single-Crystal Structure Determination\u003c/h3\u003e\n\u003cp\u003eThe structures of complexes \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e were acquired by single crystal X-ray diffraction analysis. Crystallographic data of \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e were collected at room temperature on a Bruker Smart Apex-II CCD diffractometer equipped with graphite-monochromated MoK\u003csub\u003eα\u003c/sub\u003e radiation (λ\u0026thinsp;=\u0026thinsp;0.71073 \u0026Aring;), using the \u003cem\u003eω\u003c/em\u003e scan technique. The six structures were solved by direct methods and refined anisotropically with SHELXTL software package applying the full-matrix least-squares procedures against the \u003cem\u003eF\u003c/em\u003e\u003csup\u003e2\u003c/sup\u003e values\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 data and structure refinement details for complexes \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6.\u003c/b\u003e\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=\"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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCompound\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003e3\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003e5\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003e6\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFormula\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eC\u003csub\u003e42\u003c/sub\u003eH\u003csub\u003e38\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e12\u003c/sub\u003eCd\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eC\u003csub\u003e42\u003c/sub\u003eH\u003csub\u003e38\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e12\u003c/sub\u003eCo\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eC\u003csub\u003e28\u003c/sub\u003eH\u003csub\u003e20\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003e Cl\u003csub\u003e4\u003c/sub\u003eZn\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eC\u003csub\u003e29\u003c/sub\u003eH\u003csub\u003e26\u003c/sub\u003eCl\u003csub\u003e2\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eZn\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eC\u003csub\u003e58\u003c/sub\u003eH\u003csub\u003e54\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e13\u003c/sub\u003eCl\u003csub\u003e4\u003c/sub\u003eCd\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eC\u003csub\u003e28\u003c/sub\u003eH\u003csub\u003e20\u003c/sub\u003eN\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e6\u003c/sub\u003eCl\u003csub\u003e4\u003c/sub\u003eCd\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFormula weight\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e903.16\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e849.69\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e687.63\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e634.79\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1381.65\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e734.66\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eTemperature (K)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e298(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e296(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e296(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e296(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e296(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e296(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCrystal system\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003emonoclinic\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003emonoclinic\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003emonoclinic\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eorthorhombic\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003emonoclinic\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003emonoclinic\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSpace group\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eP 2\u003csub\u003e1\u003c/sub\u003e/c\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eP 2\u003csub\u003e1\u003c/sub\u003e/c\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eP 2\u003csub\u003e1\u003c/sub\u003e/c\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003eP 2\u003csub\u003e1\u003c/sub\u003e2\u003csub\u003e1\u003c/sub\u003e2\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003eP 2\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eP2\u003csub\u003e1\u003c/sub\u003e/n\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eUnit cell dimensions\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003ea\u003c/em\u003e(\u0026Aring;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e21.6675(17)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e21.6218(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e8.4164(8)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e8.6433(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e8.3574(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e4.7878(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eb\u003c/em\u003e(\u0026Aring;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e5.8057(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5.7090(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e20.7258(19)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e13.0839(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e13.0117(14)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e13.2998(17)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003ec\u003c/em\u003e(\u0026Aring;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e15.8638(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e15.5937(8)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e16.7137(15)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e25.322(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e26.714(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e21.417(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eα\u003c/em\u003e(\u0026ordm;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eβ\u003c/em\u003e(\u0026ordm;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e104.731(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e103.484(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e91.961(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e92.042(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e96.035(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eγ\u003c/em\u003e(\u0026ordm;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e90\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eVolume/ \u0026Aring;\u003csup\u003e3\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1930.0(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1871.81(15)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2913.8(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2863.6(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2903.1(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1356.2(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eZ\u003c/em\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e2\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eDensity (calculated) (mg/mm\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.554\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.508\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.568\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.472\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1.581\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.799\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eAbsorption coefficient (mm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.638\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.533\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.255\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1.090\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.983\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.248\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eθ\u003c/em\u003e range for data collection/(\u0026ordm;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.944 to 25.242\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.937 to 25.242\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.944 to 25.242\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e2.825 to 22.799\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2.439 to 25.000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e3.063 to 24.990\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eF\u003c/em\u003e(000)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e924\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e882\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1392\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e1304\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1396\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e732\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eLimiting indices\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-28 \u0026le; \u003cem\u003eh\u003c/em\u003e \u0026le; 28, -7 \u0026le; \u003cem\u003ek\u003c/em\u003e \u0026le; 7, -21 \u0026le; \u003cem\u003el\u003c/em\u003e\u0026le; 21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-28 \u0026le; \u003cem\u003eh\u003c/em\u003e \u0026le; 27, -7 \u0026le; \u003cem\u003ek\u003c/em\u003e \u0026le; 7, -20 \u0026le; \u003cem\u003el\u003c/em\u003e\u0026le;20\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e-10 \u0026le; \u003cem\u003eh\u003c/em\u003e \u0026le; 10, -27 \u0026le; \u003cem\u003ek\u003c/em\u003e \u0026le; 25, -15 \u0026le; \u003cem\u003el\u003c/em\u003e\u0026le; 21\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e-11 \u0026le; \u003cem\u003eh\u003c/em\u003e \u0026le; 10, -17 \u0026le; \u003cem\u003ek\u003c/em\u003e \u0026le; 15, -28 \u0026le; \u003cem\u003el\u003c/em\u003e\u0026le; 31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e-9 \u0026le; \u003cem\u003eh\u003c/em\u003e \u0026le; 6, -15 \u0026le; \u003cem\u003ek\u003c/em\u003e \u0026le; 15, -31 \u0026le; \u003cem\u003el\u003c/em\u003e\u0026le; 31\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e-5 \u0026le; \u003cem\u003eh\u003c/em\u003e \u0026le; 5, -15 \u0026le; \u003cem\u003ek\u003c/em\u003e \u0026le; 15, -25 \u0026le; \u003cem\u003el\u003c/em\u003e\u0026le; 21\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eGoodness-of-fit on \u003cem\u003eF\u003c/em\u003e\u003csup\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.068\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.046\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.005\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e0.952\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0.893\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e1.035\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eFinal \u003cem\u003eR\u003c/em\u003e indices [\u003cem\u003eI\u0026thinsp;\u0026gt;\u0026thinsp;2σ(I)\u003c/em\u003e]\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0216, \u003cem\u003ewR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0564\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0379, \u003cem\u003ewR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0915\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0443, \u003cem\u003ewR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0804\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0382, \u003cem\u003ewR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0716\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0397, \u003cem\u003ewR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0770\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e1\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0224, \u003cem\u003ewR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u0026thinsp;=\u0026thinsp;0.0510\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\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\u003eSelected bond lengths (\u0026Aring;) and bond angles (\u0026ordm;) for complexes \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e\u003csup\u003e\u003cb\u003e[a]\u003c/b\u003e\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\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=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComplex 1\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.2732(10)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-O5A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.2732(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.3064(10)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.3064(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.3554(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.3554(12)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO5-Cd1-O5A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO5-Cd1-O6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e92.15(4)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO5-Cd1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e87.85(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO5-Cd1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e87.85(4)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO5A-Cd1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e92.15(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO5-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e91.87(4)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO5-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e88.13(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO5A-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e91.87(4)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO5A-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e88.13(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO6-Cd1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO6-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e84.94(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO6A-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e84.94(4)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO6A-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e95.06(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO6-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e95.06(4)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e180.00(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComplex \u003cb\u003e2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCo1-O1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.0936(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCo1-O1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.0936(11)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCo1-O6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.1034(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCo1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.1034(12)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCo1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.1763(14)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCo1-N2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.1763(14)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1-Co1-O1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e180.00(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1-Co1-O6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e87.29(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1-Co1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e92.70(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1A-Co1-O6\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e92.71(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1A-Co1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e87.30(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1-Co1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e90.71(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1-Co1-N2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e89.29(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1A-Co1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e90.71(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1A-Co1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e89.29(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO6-Co1-O6A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO6-Co1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e94.49(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO6-Co1-N2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e94.49(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO6A-Co1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e85.51(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO6-Co1-N2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e85.51(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN2-Co1-N2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComplex \u003cb\u003e3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZn1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.9563(18)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZn1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.9584(19)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.028(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.022(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3-Zn1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e95.14(8)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3-Zn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e110.85(9)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3-Zn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e110.06(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO4-Zn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e115.22(9)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO4-Zn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e108.45(9)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN2-Zn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e115.29(9)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComplex \u003cb\u003e4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.053(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZn1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.945(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eZn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.031(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eZn1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e1.936(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO4-Zn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e96.04(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO4-Zn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e106.07(13)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1-Zn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e112.96(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3-Zn1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e104.86(13)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3-Zn1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e115.00(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3-Zn1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e119.55(14)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComplex \u003cb\u003e5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.323(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.345(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.347(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-O5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.360(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.383(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.538(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.590(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd2-O7\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.216(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd2-N4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.302(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd2-N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.322(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd2-O13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.331(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd2-O11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.391(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd2-O10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.402(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e135.4(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2-Cd1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e96.8(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1-Cd1-N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e94.4(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2-Cd1-O5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e137.0(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1-Cd1-O5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e83.6(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN2-Cd1-O5\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e97.1(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2-Cd1-O8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e77.7(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN1-Cd1-O8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e89.8(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN2-Cd1-O8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e174.5(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO5-Cd1-O8\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e87.0(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2-Cd1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e88.2(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN1-Cd1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e135.8(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN2-Cd1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e85.3(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO5-Cd1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e52.80(19)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO8-Cd1-O4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e94.20(19)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2-Cd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e52.7(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1-Cd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e85.6(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN2-Cd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e85.5(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO5-Cd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e169.0(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO8-Cd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e91.25(19)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO4-Cd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e138.14(19)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO7-Cd2-N4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e126.8(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO7-Cd2-N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e86.8(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN4-Cd2-N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e100.0(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO7-Cd2-O13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e84.6(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN4-Cd2-O13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e84.8(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN3-Cd2-O13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e171.4(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO7-Cd2-O11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e149.5(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN4-Cd2-O11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e83.7(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN3-Cd2-O11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e88.7(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO13-Cd2-O11\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e99.0(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO7-Cd2-O10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e95.3(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN4-Cd2-O10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e136.3(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN3-Cd2-O10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e92.6(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO13-Cd2-O10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e88.8(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO11-Cd2-O10\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e54.76(19)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eComplex \u003cb\u003e6\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.3066(15)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-O3A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.3066(15)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.3188(15)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-O2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.3188(15)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.3707(18)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.3707(18)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3-Cd1-O3A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3-Cd1-O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e94.31(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3-Cd1-O2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e85.69(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3A-Cd1-O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e85.69(5)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3A-Cd1-O2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e94.31(5)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2-Cd1-O2A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e85.15(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e94.85(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e92.21(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e87.79(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO3A-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e94.85(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO3A-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e85.15(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2A-Cd1-N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e87.79(6)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2A-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e92.21(6)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1-Cd1-N1A\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e180.0\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e\u0026nbsp;\u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003e[a] Symmetry Code: Complex \u003cb\u003e1\u003c/b\u003e: -x, y\u0026thinsp;+\u0026thinsp;1/2, -z\u0026thinsp;+\u0026thinsp;1/2; Complex \u003cb\u003e2\u003c/b\u003e: -x, y\u0026thinsp;+\u0026thinsp;1/2, -z\u0026thinsp;+\u0026thinsp;1/2; Complex \u003cb\u003e6\u003c/b\u003e: -x, -y, -z.\u003c/p\u003e \u003cp\u003e[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. All non-hydrogen atoms were refined based on their anisotropic thermal parameters. The hydrogen atoms were located at calculated distances and refined by fixed isotropic thermal parameters as riding atoms. The crystallographic data for \u003cb\u003e1\u0026ndash;6\u003c/b\u003e are presented in Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e, selected bond lengths and angles for \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e are listed in Table\u0026nbsp;\u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e.\u003c/p\u003e"},{"header":"Results and discussion","content":"\u003cp\u003e \u003cb\u003eStructures of 1 and 2.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eSingle crystal X-ray diffraction analysis shows that complexes \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e2\u003c/b\u003e are isomorphous, belonging to monoclinic crystal system with space group P 2\u003csub\u003e1\u003c/sub\u003e/c, hence, only the structure of complex \u003cb\u003e1\u003c/b\u003e is described in detail. There are a half Cd(II) atom, one HOBA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligand, one DPE ligand and one coordinated water molecule in the asymmetric unit. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea, in the molecular structure of \u003cb\u003e1\u003c/b\u003e, two oxygen atoms from two individual HOBA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands, two coordinated water molecules and two nitrogen atoms from two DPE ligands complete the coordination environment of Cd(II) ion, which shows a distorted octahedron geometry. The Cd-N bond length is 2.3554(12) \u0026Aring;, and the Cd-O distances are 2.2732(10) and 2.3064(10) \u0026Aring;, respectively. H\u003csub\u003e2\u003c/sub\u003eOBA bears one flexible carboxyl group and one rigid carboxyl group, and this often gives rise to the formation of high-dimensional products [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. However, in compound \u003cb\u003e1\u003c/b\u003e, H\u003csub\u003e2\u003c/sub\u003eOBA is partly deprotonated and only the flexible carboxyl group is bound to the central atoms in monodentate fashion. In addition, the DPE ligands in \u003cb\u003e1\u003c/b\u003e display monodentate mode. The above mentioned factors lead to the formation of zero-dimensional complex of \u003cb\u003e1\u003c/b\u003e. Furthermore, the mononuclear molecules are linked by intermolecular C-H\u0026sdot;\u0026sdot;\u0026sdot;O hydrogen bonds between the phenyl ring and carboxyl group into a 2D network (Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003eb). The coordination mode observed in complex \u003cb\u003e1\u003c/b\u003e is very different from that in other compounds. For example, in{[Cd\u003csub\u003e2\u003c/sub\u003e(OBA)\u003csub\u003e2\u003c/sub\u003e(BIB)\u003csub\u003e2\u003c/sub\u003e](H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e7\u003c/sub\u003e}\u003csub\u003en\u003c/sub\u003e (BIB\u0026thinsp;=\u0026thinsp;1,4-bis(imidazol-1-yl)-butane)) [\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e] and [Cd(OBA)(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e3\u003c/sub\u003e]\u003csub\u003en\u003c/sub\u003e [\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], both the rigid and flexible carboxyl groups adopt bidentate-bridging mode, linking central ions to generate 1D chain.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003ea Coordination environment of Cd(II) ions in complex \u003cb\u003e1\u003c/b\u003e, all the hydrogen atoms have been deleted for clarity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eStructure of 3.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eComplex \u003cb\u003e3\u003c/b\u003e crystallizes in monoclinic P 2\u003csub\u003e1\u003c/sub\u003e/c space group. The asymmetric unit of \u003cb\u003e3\u003c/b\u003e consists of a half Zn(II) atom, one DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e and a half DPE ligand. The central Zn(II) atom has a slightly distorted tetrahedral arrangement and is surrounded by two oxygen atoms from two DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e anions, and two nitrogen atoms from different DPE molecules (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea). The Zn-O bond lengths are 1.9563(18) and 1.9584(19) \u0026Aring;, and the Zn-N distances are 2.028(2) and 2.022(2) \u0026Aring;, respectively. The pyridine rings of the DPE molecule are twisted slightly to each other as indexed by the dihedral angle of 13.3\u0026deg;. Each DPE links two Zn(II) atoms to form an infinite 1D chain with the Zn\u0026sdot;\u0026sdot;\u0026sdot;Zn distance of 13.3022(8) \u0026Aring; (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb). The DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands adopt monodentate mode, decorating the 1D chain on both sides. The 1D chains are further extended into a 2D plane through C-H\u0026sdot;\u0026sdot;\u0026sdot;O and and C-H\u0026sdot;\u0026sdot;\u0026sdot;Cl hydrogen bonding interactions (Fig.\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ec).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003ea Coordination environment of Zn(II) ions in complex \u003cb\u003e3\u003c/b\u003e, all of the hydrogen atoms have been deleted for clarity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003eb View of the 1D chain in complex \u003cb\u003e3\u003c/b\u003e, all the hydrogen atoms have been deleted for clarity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eStructure of 4.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eComplex \u003cb\u003e4\u003c/b\u003e crystallizes in orthorhombic P2\u003csub\u003e1\u003c/sub\u003e2\u003csub\u003e1\u003c/sub\u003e2\u003csub\u003e1\u003c/sub\u003e space group. As depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea, the Zn(II) atom is tetra-coordinated by two oxygen atoms of two individual CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands and two nitrogen atoms from two BPP molecules in a tetrahedron coordination environment (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea). The Zn-O distances fall into 1.936(3)-1.945(3) \u0026Aring;, and Zn-N bond lengths are 2.031(3)-2.053(3) \u0026Aring;. These data are comparable to those observed in related Zn-O/N coordination polymers [\u003cspan additionalcitationids=\"CR26\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. The BPP ligands assume \u003cem\u003ecis-\u003c/em\u003econformation, bridging adjacent Zn(II) atoms to form 1D chain along the \u003cem\u003eb\u003c/em\u003e axis with the Zn\u0026sdot;\u0026sdot;\u0026sdot;Zn separation of 13.0839(13) \u0026Aring; (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb). The neighboring chains are further linked through intermolecular C-H\u0026sdot;\u0026sdot;\u0026sdot;O interactions between the phenyl ring and carboxyl groups to afford the final 2D supramolecular architecture (Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ec).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003ea Coordination environment of Zn(II) ions in complex \u003cb\u003e4\u003c/b\u003e, all of the hydrogen atoms have been deleted for clarity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003eb View of the 1D chain in complex \u003cb\u003e4\u003c/b\u003e along \u003cem\u003eb\u003c/em\u003e direction, all of the hydrogen atoms have been deleted for clarity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eStructure of complex 5.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eComplex \u003cb\u003e5\u003c/b\u003e crystallizes in monoclinic system with space group P2\u003csub\u003e1\u003c/sub\u003e. There exist two crystallographically independent Cd(II) atoms bearing two different coordination geometries in the asymmetric unit. As illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e4\u003c/span\u003ea, Cd1 ion lies in a distorted pentagonal-bipyramidal coordination sphere, which is defined by five oxygen atoms from three CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands, and two nitrogen atoms from two BPP molecules. The equatorial plane contains four oxygen atoms (Cd1-O2\u0026thinsp;=\u0026thinsp;2.323(6), Cd1-O3\u0026thinsp;=\u0026thinsp;2.590(6), Cd1-O4\u0026thinsp;=\u0026thinsp;2.538(6) and Cd1-O5\u0026thinsp;=\u0026thinsp;2.360(5) \u0026Aring;) originating from three CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e, and one nitrogen atom from one BPP ligand (Cd1-N1\u0026thinsp;=\u0026thinsp;2.345(6) \u0026Aring; ); one nitrogen atom of BPP and one oxygen atom of CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e (Cd1-N2\u0026thinsp;=\u0026thinsp;2.347(6) and Cd1-O8\u0026thinsp;=\u0026thinsp;2.383(5) \u0026Aring; ) locate at the remaining axial positions.\u003c/p\u003e \u003cp\u003eCd2 center lies in a distorted octahedral coordination sphere formed by three oxygen atoms from two CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands, two nitrogen atoms of two BPP ligands and one coordinated water molecule. The O7, O10, O11 and N4 atoms fulfill the equatorial plane (Cd1-O7\u0026thinsp;=\u0026thinsp;2.216(5), Cd1-O10\u0026thinsp;=\u0026thinsp;2.402(6), Cd1-O11\u0026thinsp;=\u0026thinsp;2.391(6) and Cd1-N4\u0026thinsp;=\u0026thinsp;2.302(6) \u0026Aring;); and the N3 and O13 atoms occupy the axial positions (Cd1-N3\u0026thinsp;=\u0026thinsp;2.322(6) and Cd1-O13\u0026thinsp;=\u0026thinsp;2.331(5) \u0026Aring;). The deprotonated CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands exhibit chelating and \u003cem\u003esyn-anti\u003c/em\u003e bidentate bridging coordination modes; hence, a pair of Cd(II) atoms are connected to form [Cd\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e] unit with the Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd separation of 5.4307(4) \u0026Aring;. Frequently, the dinuclear cadmium unit can be formed by \u003cem\u003e\u0026micro;\u003c/em\u003e-acetato-O,O\u0026prime;, monoatomic and \u003cem\u003e\u0026micro;\u003c/em\u003e-H\u003csub\u003e2\u003c/sub\u003eO bridges and different bridging modes often result in different Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd distances. For example, the Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd distance (5.4307(4) \u0026Aring;) in \u003cb\u003e5\u003c/b\u003e is significant longer than that found for the \u003cem\u003e\u0026micro;\u003c/em\u003e-H\u003csub\u003e2\u003c/sub\u003eO bridged [Cd\u003csub\u003e2\u003c/sub\u003e(bpy)\u003csub\u003e2\u003c/sub\u003e(OAc)\u003csub\u003e4\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e] (3.6889(9) \u0026Aring;) [\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e] and cadmium-tetracarboxylate complex [Cd\u003csub\u003e2\u003c/sub\u003e(4,4'-bipy)(3,3'-bpda)\u003csub\u003e2\u003c/sub\u003e]\u003csub\u003en\u003c/sub\u003e (3,3'-bpda\u0026thinsp;=\u0026thinsp;1,1'-biphenyl-3,3'-dicarboxylate, 4,4'-bipy\u0026thinsp;=\u0026thinsp;4,4'-bipyridine) (3.050(1) \u0026Aring;) [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e], but much shorter than that observed in the bis-monoatomic bridged [Cd(pydc)(phen)]\u003csub\u003en\u003c/sub\u003e (H\u003csub\u003e2\u003c/sub\u003epydc\u0026thinsp;=\u0026thinsp;pyridine-2,3-dicarboxylic acid) (6.252(4) \u0026Aring;) [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. Furthermore, along the \u003cem\u003eb\u003c/em\u003e axis, the [Cd\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e] units are connected by the BPP ligands to give the formation of 1D double chain with the Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd separation of 13.0117(14) \u0026Aring; (Fig.\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e4\u003c/span\u003eb).\u003c/p\u003e \u003cp\u003eCd(II) complexes based on phenoxyacetic acid derivatives and BPP ligands have been previously reported. For example, in [Cd\u003csub\u003e4\u003c/sub\u003e(DPA)\u003csub\u003e8\u003c/sub\u003e(BPP)\u003csub\u003e4\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e]\u003csub\u003en\u003c/sub\u003e, the HDPA shows bidentate bridging and monoatomic bridging fashions [\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. These differences imply that the substituent group plays an important role in directing the final structure.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eStructure of complex 6.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eX-ray analysis of complex \u003cb\u003e6\u003c/b\u003e reveals that it crystallizes in monoclinic space group P2\u003csub\u003e1\u003c/sub\u003e/n. The asymmetric unit contains one Cd(II) atom, one DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligand and a half DPE molecule. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003ea, each Cd(II) center is six-coordinated in a distorted octahedral geometry, which is defined by four oxygen atoms from four DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands, and two nitrogen atoms from two DPE ligands. The equatorial plane is composed of four oxygen atoms originating from four bridging DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e anions; two nitrogen atoms of two DPE occupy the remaining axial positions. The Cd-N bond lengths are 2.3707(18) \u0026Aring; and the Cd-O ones are in the range of 2.3066(15) \u0026minus;\u0026thinsp;2.3188(15) \u0026Aring;, respectively. In addition, the coordination angles around Cd ion span from 85.15(6) to 180.0 \u0026ordm;. These structure parameters are in the normal range for similar Cd-O/ N systems [\u003cspan additionalcitationids=\"CR32 CR33 CR34\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e anions adopting \u003cem\u003esyn-anti\u003c/em\u003e bidentate bridging coordination mode, link neighboring Cd(II) atoms to form [Cd\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e] unit with the Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd separation of 4.7878(6) \u0026Aring;. It is interesting to note that the Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd value in \u003cb\u003e5\u003c/b\u003e is longer than that observed in \u003cb\u003e6\u003c/b\u003e, the difference may arise from that the Cd(II) atoms in \u003cb\u003e6\u003c/b\u003e are bridged by two carboxyl groups, while in \u003cb\u003e5\u003c/b\u003e, only one carboxyl group acts as bridge between the two Cd(II) atoms. The dinuclear cadmium units are linked by DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands to form one-dimensional chain along \u003cem\u003ea\u003c/em\u003e direction (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003eb). Furthermore, The exo-bidentate DPE may be regarded as a pillar of the [Cd\u003csub\u003e2\u003c/sub\u003e(DPA)\u003csub\u003e4\u003c/sub\u003e]\u003csub\u003en\u003c/sub\u003e chain through \u003cem\u003etrans\u003c/em\u003e coordinating to the [Cd\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e] units of different chains along the direction of the \u003cem\u003eb-\u003c/em\u003eaxis with the Cd\u0026sdot;\u0026sdot;\u0026sdot;Cd separation of 14.1353(16) \u0026Aring;, resulting the formation of 2D layer (Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e5\u003c/span\u003ec).\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cb\u003eStructural comparison of complexes 1\u0026ndash;6.\u003c/b\u003e \u003c/p\u003e \u003cp\u003eThe structural differences of complexes \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e indicate the role of central atoms and ligands with different substituent groups in fabricating metal-organic compounds (Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e). Though zinc and cadmium fall into the identical periodic group, they show different coordination natures. In complexes \u003cb\u003e3\u003c/b\u003e and \u003cb\u003e4\u003c/b\u003e, the Zn(II) atoms are tetra-coordinated with two oxygen atoms and two nitrogen atoms. The carboxyl groups of DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e and CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligands exhibits monodentate fashion in both complexes. However, in \u003cb\u003e1\u003c/b\u003e, \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e6\u003c/b\u003e, the Cd(II) atoms are hexa- or hepta-coordinated by oxygen and nitrogen atoms from the carboxylate acids, N-donor ligands and coordinated water molecules. On the other hand, the difference between HDPA and HCPA lies in that HDPA has an additional chlorine atom at the 4-position compared to HCPA, and this distinction has a subtle effect on the coordination mode of carboxyl groups. Though HDPA and HCPA share the same coordination fashion in complexes \u003cb\u003e3\u003c/b\u003e and \u003cb\u003e4\u003c/b\u003e, they exhibit different coordination modes in complexes \u003cb\u003e5\u003c/b\u003e and \u003cb\u003e6\u003c/b\u003e. In complex \u003cb\u003e5\u003c/b\u003e, the CPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligand shows bidentate bridging and chelating fashion, bridging hexa- or hepta-coordinated Cd(II) atoms to generate 1D double chain. However, the DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e ligand in complex \u003cb\u003e6\u003c/b\u003e assumes bidentate bridging mode, linking adjacent Cd(II) ions to form 1D chain. The effect of substituent on structures can also be found in complexes \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e6\u003c/b\u003e. The H\u003csub\u003e2\u003c/sub\u003eOBA ligand simultaneously bears flexible and rigid carboxyl groups, with multiple coordination sites, which facilitate the formation of high-dimensional coordination complexes. However, the rigid carboxyl group does not participate in coordination, and the flexible carboxyl group adopts monodentate mode in complex \u003cb\u003e1\u003c/b\u003e. Moreover, the DPE ligands coordinate to the central atoms in monodentate mode, which differs from that observed in \u003cb\u003e3\u003c/b\u003e and \u003cb\u003e6\u003c/b\u003e. These factors hinder the formation of high dimensional network, leading to 0D mononuclear structure of \u003cb\u003e1\u003c/b\u003e. The present results further illustrate that central atoms and organic ligands with different substituent groups have significant influence on the final structures of the complexes.\u003c/p\u003e\n\u003ch3\u003eThermogravimetric analysis\u003c/h3\u003e\n\u003cp\u003eThermogravimetric (TG) measurements of crystalline compounds \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e were carried out in a nitrogen atmosphere from 20 to 700\u0026deg;C (Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e6\u003c/span\u003e). For compound \u003cb\u003e1\u003c/b\u003e, a moderate mass decline of 4.12% (calculated 3.99%) was noted between 110 and 150\u0026deg;C, attributed to the loss of two coordinated water molecules. The dehydrated complex started to decompose above 230\u0026deg;C, ultimately yielding CdO (observed 13.91%; calculated 14.22%) as the residue. Compound \u003cb\u003e2\u003c/b\u003e released one coordinated water molecule between 100 and 150\u0026deg;C, with an observed mass loss of 4.05% (calculated 4.24%). A subsequent rapid mass decrease related to organic ligand decomposition began at 235\u0026deg;C, with the process finally giving CoO (observed 8.52%; calculated 8.82%) as the end product. Only one major mass loss was detected for complexes \u003cb\u003e3\u003c/b\u003e, \u003cb\u003e4\u003c/b\u003e, and \u003cb\u003e6\u003c/b\u003e. These materials remained stable up to approximately 220\u0026deg;C, after which substantial decomposition took place, corresponding to the elimination of their organic components. The residual masses matched well with the formation of ZnO (observed 11.93%; calculated 11.84%) for \u003cb\u003e3\u003c/b\u003e, ZnO (observed 11.90%; calculated 12.82%) for \u003cb\u003e4\u003c/b\u003e and CdO (observed 17.98%; calculated 17.48%) for \u003cb\u003e6\u003c/b\u003e. In the case of compound \u003cb\u003e5\u003c/b\u003e, a minor mass reduction of 1.35% (calculated 1.30%) occurred between 120 and 160\u0026deg;C, associated with the removal of one coordinated water molecule. The resulting dehydrated solid remained stable until 270\u0026deg;C, beyond which ligand decomposition occurred, leaving CdO (observed 18.51%; calculated 18.59%) as the final product.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eStructural comparison for complexes \u003cb\u003e1\u003c/b\u003e\u0026ndash;\u003cb\u003e6.\u003c/b\u003e\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=\"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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCompound\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCentral atom\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eCarboxylate ligand\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eCoordination polyhedron\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eCoordination fashion\u003c/p\u003e \u003cp\u003eof the carboxyl group\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003edimensionality\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c7\"\u003e \u003cp\u003eSecondary interaction\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e1\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCd\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4-carboxylphenoxyacetic acid (H\u003csub\u003e2\u003c/sub\u003eOBA)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eoctahedron\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003emonodentate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0D\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eH-bonding\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e2\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCo\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4-carboxylphenoxyacetic acid (H\u003csub\u003e2\u003c/sub\u003eOBA)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eoctahedron\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003emonodentate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e0D\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eH-bonding\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e3\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZn\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2,4-dichlorophenoxyacetic acid (HDPA)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etetrahedron\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003emonodentate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1D linear chain\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eH-bonding\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e4\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eZn\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2-chlorophenoxyacetic acid (HCPA)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003etetrahedron\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003emonodentate\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1D linear chain\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e \u003cp\u003eH-bonding\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e5\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCd\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2-chlorophenoxyacetic acid (HCPA)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eoctahedron, pentagonal bipyramid\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003echelating, bidentate bridging\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e1D double chain\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003e6\u003c/b\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eCd\u003csup\u003e2+\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e2,4-dichlorophenoxyacetic acid (HDPA)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003eoctahedron\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c5\"\u003e \u003cp\u003ebidentate bridging\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c6\"\u003e \u003cp\u003e2D layer\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c7\"\u003e\u0026nbsp;\u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e\n\u003ch3\u003ePhotoluminescence properties\u003c/h3\u003e\n\u003cp\u003eCoordination polymers with d\u003csup\u003e10\u003c/sup\u003e closed-shell electronic configuration metal ions can incorporate ligands with specific fluorescent properties, and their rigid frameworks can reduce non-radiative relaxation, thereby enhancing fluorescence emission. As a result, coordination polymers are regarded as a class of promising luminescent materials. Moreover, the synergistic functionalization of permanent porosity and luminescent properties endows coordination polymers with significant potential for applications in fluorescence. As previously reported, the free ligands BPP and DPE show fluorescence in the solid state, with emission peaks observed at 468 nm and 530 nm, respectively [\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e, \u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e]. These emissions can be assigned to π* \u0026rarr; π or π* \u0026rarr; n electronic transitions [\u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. As shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e7\u003c/span\u003e, compounds \u003cb\u003e3\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e exhibit distinct fluorescent emission bands: 470 nm (λex\u0026thinsp;=\u0026thinsp;285 nm) for \u003cb\u003e3\u003c/b\u003e, 445 nm (λex\u0026thinsp;=\u0026thinsp;330 nm) for \u003cb\u003e4\u003c/b\u003e, 441 nm (λex\u0026thinsp;=\u0026thinsp;330 nm) for \u003cb\u003e5\u003c/b\u003e, and 465 nm (λex\u0026thinsp;=\u0026thinsp;285 nm) for \u003cb\u003e6\u003c/b\u003e. Compared with the emissions of the free ligands, complexes \u003cb\u003e3\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e show blue shifts of approximately 60 nm, 23 nm, 27 nm and 65 nm, respectively. In compounds containing Zn(II) or Cd(II) ions with d\u0026sup1;⁰ configuration, emission typically does not originate from metal-to-ligand charge transfer (MLCT) or ligand-to-metal charge transfer (LMCT), since d\u0026sup1;⁰ metal ions are generally neither easily oxidized nor reduced [\u003cspan additionalcitationids=\"CR41\" citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e]. Therefore, the emission of \u003cb\u003e3\u003c/b\u003e\u0026ndash;\u003cb\u003e6\u003c/b\u003e is likely attributed to intraligand charge transfer. The observed blue shifts and variations in emission intensity among these complexes are probably due to differences in the coordination modes of the aromatic carboxylate ligands and the distinct coordination environments of the metal centers [\u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003c/p\u003e"},{"header":"Conclusions","content":"\u003cp\u003eSix Zn(II)/Cd(II) and Co(II) complexes have been constructed using R-phenoxyacetic acids and auxiliary N-donor ligands under hydrothermal conditions. Although these compounds are obtained under similar synthetic conditions, the different coordination fashions of the carboxylic acids and N-donor ligands result in various molecular architectures ranging from 0D mononuclear molecule, 1D chain to 2D layer. The structural diversity between these complexes indicates that organic ligands with different substituent groups and central metals play important roles in the construction of complexes. In addition, the hydrogen bond interactions are conducive to the formation of supramolecular structure. These results may give us some inspiration in the controllable preparation of desired coordination polymers tailed with specific functions and structures.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003cstrong\u003eConflict of interest\u003c/strong\u003e \u003cp\u003eThe authors declare no competing interests.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eFunding\u003c/h2\u003e \u003cp\u003eThis work was supported by Scientific Research Foundation of Anhui Provincial Education Department (KJ2019A0597 and KJ2020A0022).\u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eStudy conception and experimental design were by Yonghong Zhou and Longfeng Li. Experimental work, data collection and analyses were by Yonghong Zhou and Yun Xu. The original draft was prepared by Yonghong Zhou. All authors took part in revising the manuscript, and all have read and approved the final draft.\u003c/p\u003e\u003ch2\u003eData Availability\u003c/h2\u003e\u003cp\u003eCCDC 2503460-2502465 for **1** - **6** contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via the internet at http://www.ccdc.cam.ac.uk/data_request/cif, or by e-mailing [[email protected]](mailto:[email protected]) .\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eYuan F, Du YT, Shen SS, Hu HM, Zhou CS, Qiao CF, Cao BY, Singh A, Kumar A (2025) Luminescent properties and hirshfeld surface analyses of two new 3D Zn(II) coordination polymers assembled from isomeric terpyridyl carboxylate derivative and terephthalate ligands. 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Cryst Growth Des 13(7):3177\u0026ndash;3187\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-chemical-crystallography","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jocc","sideBox":"Learn more about [Journal of Chemical Crystallography](http://link.springer.com/journal/10870)","snPcode":"10870","submissionUrl":"https://submission.nature.com/new-submission/10870/3","title":"Journal of Chemical Crystallography","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Crystal structure, Coordination polymer, Zinc(II) complex, Cobalt(II) complex, Cadmium(II) complex","lastPublishedDoi":"10.21203/rs.3.rs-8392230/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8392230/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eSix novel Zn(II), Cd(II) and Co(II) mixed-ligand coordination complexes, namely, Cd(HOBA)\u003csub\u003e2\u003c/sub\u003e(DPE)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003e1\u003c/b\u003e), Co(HOBA)\u003csub\u003e2\u003c/sub\u003e(DPE)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)\u003csub\u003e2\u003c/sub\u003e (\u003cb\u003e2\u003c/b\u003e), [Zn(DPA)\u003csub\u003e2\u003c/sub\u003e(DPE)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e3\u003c/b\u003e), [Zn(CPA)\u003csub\u003e2\u003c/sub\u003e(BPP)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e4\u003c/b\u003e), [Cd\u003csub\u003e2\u003c/sub\u003e(CPA)\u003csub\u003e4\u003c/sub\u003e(BPP)\u003csub\u003e2\u003c/sub\u003e(H\u003csub\u003e2\u003c/sub\u003eO)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e5\u003c/b\u003e), and [Cd(DPA)\u003csub\u003e2\u003c/sub\u003e(DPE)]\u003csub\u003en\u003c/sub\u003e (\u003cb\u003e6\u003c/b\u003e) (H\u003csub\u003e2\u003c/sub\u003eOBA\u0026thinsp;=\u0026thinsp;4-carboxylphenoxyacetic acid, HDPA\u0026thinsp;=\u0026thinsp;2,4-dichlorophenoxyacetic acid, HCPA\u0026thinsp;=\u0026thinsp;2-chlorophenoxyacetic acid, DPE\u0026thinsp;=\u0026thinsp;1,2-di(pyridin-4-yl)ethylene, BPP\u0026thinsp;=\u0026thinsp;1,3-bis(4-pyridyl)propane) have been synthesized hydrothermally by the self-assembly of R-phenoxyacetic acid (R\u0026thinsp;=\u0026thinsp;2,4-dichloro, 2-chloro and 4-carboxyl), N-donor ligands and Zn(II), Cd(II) or Co(II) salts. Single crystal X-ray analyses reveal that in complexes \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e2\u003c/b\u003e, the H\u003csub\u003e2\u003c/sub\u003eOBA and DPE act as terminal ligands, generating 0D Cd(II) and Co(II) mononuclear molecules. Complexes \u003cb\u003e3\u003c/b\u003e and \u003cb\u003e4\u003c/b\u003e both show 1D chain structures, where the four-coordinated Zn(II) ions are bridged by DPE and BPP, respectively. For complex \u003cb\u003e5\u003c/b\u003e, the six- and seven-coordinated Cd(II) ions are interconnected through carboxyl groups to form [Cd\u003csub\u003e2\u003c/sub\u003e(CPA)\u003csub\u003e4\u003c/sub\u003e] building units, which are subsequently extended by BPP ligands into 1D chains. In complex \u003cb\u003e6\u003c/b\u003e, adjacent Cd(II) ions are bridged by DPA\u003csup\u003e\u0026minus;\u003c/sup\u003e anions to form a 1D linear chain. Through the bridging of DPE ligands, the 1D chains undergo dimensional expansion and eventually evolve into 2D supramolecular architectures. Furthermore, the thermal stabilities and fluorescence properties of these complexes have also been investigated.\u003c/p\u003e","manuscriptTitle":"From zero-dimensional complexes to two-dimensional coordination polymers adjusted by metal ions or ligand substituent groups","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-03 05:49:17","doi":"10.21203/rs.3.rs-8392230/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2026-03-06T20:10:47+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-27T20:34:16+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-23T21:10:24+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"169020787500536097803429573197647127492","date":"2026-02-12T16:02:56+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"94380123871746673493485199286766762342","date":"2026-02-11T08:06:03+00:00","index":"hide","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2026-02-09T13:18:43+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"18176685543874317644434373483992767937","date":"2026-01-31T14:15:11+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2026-01-30T17:01:23+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2025-12-19T05:27:07+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2025-12-19T05:26:42+00:00","index":"","fulltext":""},{"type":"submitted","content":"Journal of Chemical Crystallography","date":"2025-12-18T07:06:23+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"journal-of-chemical-crystallography","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"jocc","sideBox":"Learn more about [Journal of Chemical Crystallography](http://link.springer.com/journal/10870)","snPcode":"10870","submissionUrl":"https://submission.nature.com/new-submission/10870/3","title":"Journal of Chemical Crystallography","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"cf3b4942-625a-429c-818a-69e56f8eb990","owner":[],"postedDate":"February 3rd, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"under-review","subjectAreas":[],"tags":[],"updatedAt":"2026-04-23T14:39:22+00:00","versionOfRecord":[],"versionCreatedAt":"2026-02-03 05:49:17","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8392230","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8392230","identity":"rs-8392230","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}