Synthesis, crystal structure, and characterization of two new end-to-end 1D pseudohalide bridged manganese(III) complexes

Synthesis, crystal structure, and characterization of two new end-to-end 1D pseudohalide bridged manganese(III) complexes | 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 Synthesis, crystal structure, and characterization of two new end-to-end 1D pseudohalide bridged manganese(III) complexes Uttam Mandal, Corrado Rizzoli, Bikash Chakraborty, Srikanta Karmakar, and 3 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-3281596/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 27 Jan, 2024 Read the published version in Transition Metal Chemistry → Version 1 posted 10 You are reading this latest preprint version Abstract Two new Manganese (III) Schiff base complexes MnL 2 N 3 ( 1 ) and MnL 2 NCS ( 2 ) where HL is 4-bromo-2-[( Z )-{[2-(thiophen-2-yl)ethyl]imino}methyl]phenol) were synthesized and characterized by UV–Vis. absorption spectra, FT-IR, photoluminescence (PL) emission spectra, TGA Analyses, and single-crystal X-ray diffraction technique. Structural studies reveal that the metal sites in all complexes are six-coordinated by two phenoxy oxygen and two imine nitrogen atoms of two moles of Schiff base ligand, HL. The geometry around the metal center is twisted octahedral geometry with a MnN 4 O 2 (for 1 ) and MnN 3 O 2 S (for 2 ) chromophore. Hirshfeld surfaces associated with 2D fingerprint plots have been used to analyze intermolecular interactions in crystal packing. Computational study using Density Functional Theory (DFT) has been done (for 1 ) to elucidate the structural information and energy gap calculation between HOMO & LUMO. Crystal packing of both complexes shows the interchain π \(\cdots\) π stacking interactions between one-dimensional chains. Manganese (III) Schiff base complex Crystal structure thiocyanate azide Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Introduction Schiff base, a remarkable group of organic molecules, has appeared as a commonly used chelating ligand for the formation of transition metal complexes [ 1 – 7 ]. For their fascinating properties in building competent catalysts[ 8 – 11 ], promising magnetic materials[ 12 – 15 ], vital pharmaceuticals[ 16 ], optoelectronic gadgets[ 17 ], bio-mimetic homolog[ 18 ] and so on, the newly produced Schiff bases and their complex compounds show considerable dedication to the research community[ 19 – 24 ] . The coordination compound of manganese with a wide variety of Schiff base ligands has extensively been studied as a topic of great attention in bioinorganic chemistry[ 25 – 28 ]. Redox enzymes containing manganese play important dynamic role in nature. Biological features of wide variety of Mn(III) complexes that can imitate the structural aspects of several metalloprotein, redox, and non-redox proteins [ 29 , 30 ]. Many of these compounds have also been found to have attractive catalytic [ 31 – 33 ] and magnetic[ 34 – 36 ] properties. The preparation and structural elucidation of such complexes has increased demand due to their biological relevance [ 37 ], particularly in imitating the compound, such as, in photosystem II[ 38 – 40 ]. The pseudohalide anions (like azide and thiocyanate) can coordinate with metal ions as bridging linkers or as terminal ligands. They exhibit a wide range of coordination modes as bridging ligands. Among them, end-on(µ 1,1 –N 3 )[ 20 , 23 , 24 , 41 , 42 ] and end-to-end(µ 1,3 –N 3 )[ 20 , 23 , 43 ]bridging is the most widespread (Scheme 1 ). Although the coordination mode of an azido ligand to a particular metal ion is difficult to predict, it is believed that the steric and electronic properties of the co-ligands play a significant influence in this process. This paper describes the synthesis and characterization of two novel manganese (III) compounds with Schiff base salen-type ligands and pseudohalide as bridging ligands. Experimental Section Materials and instruments All compounds were reagent grade and were used as received from Sigma-Aldrich or Merck Companies without additional purification. Caution!!! Metal complexes with organic ligands in the presence of perchlorate and azide are potentially explosive, even though no difficulties were encountered in this study. Only a small amount of the material should be prepared, and it must be handled carefully. The UV–Vis. absorption spectra of the prepared complexes were measured by UV–Vis. Spectrophotometer (PerkinElmer model: lambda25) at a wavelength ranging from 200nm to 700nm. The photoluminescence emission spectra were measured by PL a spectrofluorimeter: Horiba Fluorolog 3–22 luminescence spectrometer. Both the absorption and PL emission spectra were measured in the solution phase. 10 mg of the prepared samples were mixed in 10 ml of methanol. Then the mixture was sonicated for 30 min to obtain homogenous solution. The Fourier-transform infrared spectroscopy (FTIR) spectra were taken between 500 cm − 1 and 4000 cm − 1 using a spectrometer (PerkinElmer, spectrum 2). The thermogravimetric analysis (TGA) measurements were carried out using a TGA analyzer (Perkin-Elmer TGA 4000). Here, the samples were heated from room temperature to 750 ◦ C at a rate of 10 ◦ C min − 1 , under an N 2 flux of 30 mL min − 1 . Synthesis Preparation of Ligand 5-Bromosalicylaldehyde (201 mg) in a methanolic solution (20 mL) was added to a methanolic solution (20 mL) of 2-thiopheneethylamine (127 mg). The mixture was refluxed for 3 hours. The yellow solution was used to prepare the complex without isolating the ligand (HL). Preparation of complexes1-2 Complexes 1 and 2 were prepared by mixing metal perchlorate, Schiff base ligand HL, and azide (for 1 ) or thiocyanate (for 2 ) in mixture of 60% acetonitrile and 40% ethanol for 1 and acetonitrile for 2 in a 1:1:1 molar ratio, followed by gradual evaporation. Mn (ClO 4 ) 2 ∙6H 2 O (360 mg, 1 mmol) dissolved in 10 ml of mixture of 60% acetonitrile and 40% ethanol was added dropwise to a solution of Schiff base ligand, HL (620mg, 2mmol) in a mixture of 60% acetonitrile and 40% ethanol at room temperature with steady stirring. Sodium azide (65 mg, 1 mmol) dissolved in a 4 mL mixture of 60% acetonitrile and 40% ethanol was progressively added to the resultant stirred solution. Stirring was continued for about 45 minutes, after which the solution was filtered and placed in a beaker open to the atmosphere for slow evaporation. Dark brown crystals of 1 appeared after 5–7 days. The crystals were collected after washing with a little mixture of 60% acetonitrile and 40% ethanol and drying. The preparation of complex 2 followed the same synthetic procedure as that of complex 1. For 2, acetonitrile and ammonium thiocyanate (76 mg, 1 mmol) respectively were used in place of mixture of 60% acetonitrile l and 40% ethanol and Sodium azide (65 mg, 1 mmol). Brown crystals were found after 5–7 days. For compound 1 : Yield 0.47 g (65%). Anal. Calc. C 43.65%, H 3.09%, N 9.79%. Found. C 43.67%, H 3.09%, N 9.81%. IR (KBr pellet, cm − 1 ) 1617(s), 2058(s), 1301(s), 484(w). For compound 2 : Yield 0.51 g (70%). Anal. Calc. C 44.33%, H 3.03%, N 5.74% Found: C 44.22%, H 3.01%, N 5.68%; IR (KBr pellet, cm − 1 ) 1615(s), 2088(s), 1294(s), 483(w). X-ray crystallographic studies Single crystal X-ray intensity data of 1 and 2 were collected on a Bruker DUO VENTURE diffractometer equipped with graphite monochromated Mo K α radiation (λ = 0.71073 Å) at 294(2) K. Data collection and reduction were carried out using the APEX3 and SAINT packages[ 44 ]. Multi-scan absorption correction using the SADABS software[ 44 ] was applied to the intensity data. The structures were solved by direct methods using SHELXT[ 45 ] and refined with full-matrix least-squares on F 2 on all unique reflections using SHELXL-2019/3[ 46 ]. In both complexes, the thiophene rings were found to be disordered over two orientations, sharing the C10/C12/C13 and C23/C25/C26 carbon atoms and rotated by 180° about the C9−C10 and C22−C23 bonds, with refined occupancy ratios of 0.760(7):0.240(0) and 0.627(6):0.373(6) for 1 , and 0.530(5):0.470(5) and 0.828(6):0.172(6) for 2 . During the refinement of the disordered rings, EXYZ and EADP restraints were applied. All hydrogen atoms were placed geometrically and refined using a riding atom approximation, with C − H = 0.93–0.97 Å, and with U iso (H) = 1.2 U eq (C). The crystal of both compounds were refined as a 2-component inversion twin using the matrix [-1 0 0, 0–1 0, 0 0–1] with a volume fraction for the two domains of 0.015(8):0.985(8) and 0.014(7):0.986(7) for 1 and 2 , respectively. All figures were drawn using the ORTEP-3 [ 47 ]and SCHAKAL-99 [ 48 ] programs. Table 1 Crystallographic Data and Structural Refinement of Complexes 1and 2 1 2 Formula C 26 H 22 Br 2 MnN 5 O 2 S 2 C 27 H 22 Br 2 MnN 3 O 2 S 3 Formula weight 715.36 731.41 Crystal system orthorhombic orthorhombic Space group Pca 2 1 Pca 2 1 a (Å) 16.5777(3) 16.5423(4) b (Å) 13.1133(4) 13.2615(3) c (Å) 12.7825(4) 13.4661(3) \(\alpha\) (˚) \(\beta\) (˚) \(\gamma\) (˚) V (Å 3 ) 90 90 90 2778.77(13) 90 90 90 2954.14(12) Z 4 4 D c (g cm − 3 ) 1.710 1.645 µ (mm − 1 ) 3.535 3.394 F (000) 1424 1456 λ (Mo K α ) 0.71073 0.71073 θ range (°) 1.98–25.25 1.97–25.50 T (K) 294(2) 294(2) Index ranges -19 ≤ h ≤ 19 − 15 ≤ k ≤ 15 –15 ≤ l ≤ 15 -20 ≤ h ≤ 20 − 16 ≤ k ≤ 16 –16 ≤ l ≤ 16 Reflections collected 71601 89268 Unique reflections 5004 5407 Reflections I > 2σ( I ) 4839 5280 R int 0.038 0.031 R ( I > 2σ( I ) ) 0.022 0.020 w R 2 0.056 0.053 Goodness-of-fit ( F 2 ) 1.045 1.028 Δ ρ max/Δ ρ min (e Å −3 ) 0.41 / -0.40 0.37 / -0.31 Table 2 Selected bond distances (Å) and angles (°) of Complexes 1 and 2 1 2 Mn1 − O1 1.869(2) Mn1 − O1 1.856(2) Mn1 − O2 1.861(2) Mn1 − O2 1.866(2) Mn1 − N1 2.052(3) Mn1 − N1 2.047(3) Mn1 − N2 2.041(3) Mn1 − N2 2.054(3) Mn1 − N3 2.234(3) Mn1 − N3 2.183(3) Mn1 − N5 i 2.356(4) Mn1 − S3 ii 2.8022(10) O1 − Mn1 − O2 179.82(12) O1 − Mn1 − O2 172.31(11) O1 − Mn1 − N1 89.97(10) O1 − Mn1 − N1 89.60(10) O1 − Mn1 − N2 90.10(11) O1 − Mn1 − N2 89.61(10) O1 − Mn1 − N3 90.03(12) O1 − Mn1 − N3 95.54(12) O1 − Mn1 − N5 i 88.84(14) O1 − Mn1 − S3 ii 95.21(8) O2 − Mn1 − N1 89.86(10) O2 − Mn1 − N1 90.13(10) O2 − Mn1 − N2 90.07(11) O2 − Mn1 − N2 90.28(10) O2 − Mn1 − N3 90.00(12) O2 − Mn1 − N3 92.21(11) O2 − Mn1 − N5 i 91.12(14) O2 − Mn1 − S3 ii 77.13(8) N1 − Mn1 − N2 175.46(11) N1 − Mn1 − N2 177.17(10) N1 − Mn1 − N3 89.53(13) N2 − Mn1 − N3 92.21(11) N1 − Mn1 − N5 i 87.94(13) N1 − Mn1 − S3 ii 93.26(8) N2 − Mn1 − N3 95.01(13) N1 − Mn1 − N3 90.57(11) N2 − Mn1 − N5 i 87.52(13) N2 − Mn1 − S3 ii 84.11(7) N3 − Mn1 − N5 i 177.24(15) N3 − Mn1 − S3 ii 168.61(10) Symmetry codes: (i) 0.5-x, y, -0.5 + z; (ii) 0.5-x, y, 0.5 + z. Computational details In this study, Crystal Explore 21.5[ 49 ] software and the Crystallography information file of both complexes 1 and 2 were used to compute Hirshfeld surfaces (HS) and their corresponding 2D fingerprint plots (FP). These tools allowed the measurement and exploration of the many non-covalent intermolecular interactions in the crystal lattice. By using the normalized contact distance \({d}_{norm}\) , which took into account the separation between the surface spot and the nearest internal nucleus (d i ) or external nucleus \({(d}_{e}\) ), as well as the van der Waals radii of the atom (as shown by the Eq. 1 ) facilitated the identification of the areas that were especially important for intermolecular interactions [ 50 ]. $${d}_{norm}= \frac{{d}_{e}-{r}_{i}^{vdw}}{{r}_{e}^{vdw}} + \frac{{d}_{i}-{r}_{i}^{vdw}}{{r}_{i}^{vdw}}$$ 1 When intermolecular interactions were, respectively, shorter or longer than van der Waals radii(vdW) of the atoms, the values of the \({d}_{norm}\) were negative or positive [ 51 ]. A red-blue-white color combination was used to map the \({d}_{norm}\) values onto the Hirshfeld surface, where red regions represent closer interactions and a negative \({d}_{norm}\) value, blue regions represent longer contacts and a positive \({d}_{norm}\) value, and white regions represent contacts that were exactly separated by the van der Waals distance and had a zero \({d}_{norm}\) value. Hirshfeld surfaces were traced with \({d}_{norm}\) varying from − 0.656 (red) to 1.705 (blue) for 1 and from − 0.518 (red) to 1.807 (blue) for 2 , respectively and for shape index varying from − 0.997 (concave) to 0.999(convex) for 1 and from − 0.993(concave) to 0.998(convex) for 2 and for curvedness varying from − 3.838 (flat) to 0.358(singular) for 1 and from − 3.558 (flat) to 0.409 (singular) for 2 shows in Fig. 3 . Crystal voids were estimated utilizing Crystal Explorer 21.5[ 49 ] software. For Density Functional Theory (DFT) computation, we performed a ground state geometry optimization process for the complex 1 based on X-ray diffraction data, and a fragment was chosen to obtain a perfect symmetry around the central metal ion with complete coordination as observed in the ligand cluster using B3LYP/6-31G(d,p) basis set in Gaussian 09 program [ 52 , 53 ]. The DFT calculation was performed by taking pentadentate Mn system ligand clusters. Results and Discussions Synthesis and Characterization Schiff base and pseudohalide ligand are reacted with \({\text{M}\text{n}\left(\text{C}\text{l}{\text{O}}_{4}\right)}_{2}\bullet 6{\text{H}}_{2}\text{O}\) in mixture of 60% acetonitrile and 40% ethanol for 1 and acetonitrile for 2 at room temperature to produce the Mn(III) complexes in a satisfactory yield (Scheme 2 ). Both of these complexes form crystals in the orthorhombic space group P ca \({2}_{1}\) with manganese centres arranged in distorted octahedral geometry and coupled to one another by µ 1,3 bridging pseudohalide (azide for 1 and thiocyanate for 2 ) anions. The composition of complexes are predicted based on their X-ray crystallography, elemental analysis, Hirshfeld surface analysis and various spectroscopic results. Description of the structures The Mn(III) ions, octahedrally surrounded by four donor atoms (N2O2) from the Schiff base ligand constitute the equatorial plane and two (N, N) atoms from the azide or (N, S) atoms from thiocyanate ligands for compounds 1 and 2 , respectively. In contrast to the basal bond distances, which are within the range seen for structurally characterized manganese(III) complexes [ 54 – 60 ], the axial bond distances are significantly larger (Table 1 ). The elongation of axial bonds can be explained in terms of Jahn–Teller distortion[ 61 ]. Hirshfeld surface analysis(HSA) Hirshfeld surface analysis can offer a thorough view of the intermolecular interactions inherent in a molecule. Hirshfeld surface of complexes 1–2 mapped over \({d}_{norm}\) (two distinct views), shape index and curvedness are shown in Fig. 3 labelled as (1a,1b,1c) and (2a,2b,2c), respectively. The seven different red spots on the Hirshfeld surface area mapped over \({d}_{norm}\) of complex 1 (Fig. 3 - 1 a) confirmed the existence of C − H∙∙∙N/N∙∙∙H − C type weak hydrogen bonds, H⋯Br and N ⋯ Mn/Mn⋯N interactions. Likewise, analysis of \({d}_{norm}\) Hirshfeld surface for complex 2 (Fig. 3 - 2 a) indicates that seven red spots signify the existence of C–H⋯Br, C–H⋯S type weak hydrogen bonds and Mn⋯S/S⋯Mn interactions. N⋯Mn/Mn⋯N interactions for 1 and Mn⋯S/S⋯M interactions for 2 are primarily responsible for creating the one-dimensional chain molecular structure[ 62 ]. Orange and blue adjacent triangular regions (bow tie design) are visible in the shape index function for both complexes, which signifies the existence of \(\pi \cdots \pi\) stacking interactions. The detection of patches on flat surfaces on curvedness Hirshfeld Surface also confirms the existence of π ⋯π interactions. In Table 3, there are numerical values showing the molecule volume (V H ), globularity (G), asphericity(Ω), and surface area (A H ).Compared to complex 1 , complex 2 has more molecular volume, globularity, and asphericity but less surface area. Complexes 1 and 2 have globularity values (0.675 and 0.711) that are less than unity, indicating the greatest deviance from a spherical surface[ 63 ]. Asphericity (Ω) is a metric for molecular anisotropy, and value of complex 1 ( 0.102) is relatively lower than that of the complex 2 (0.124), indicating a lesser departure from isotropy in the former[ 64 ]. 2D fingerprint plots of the both complexes are displayed in Fig. 4 . A plot of d i versus d e is a 2D fingerprint plot which recognizes the existence and amount of different type of intermolecular interactions. The H∙∙∙H intermolecular interactions play a significant role in the crystal packing of both complexes 1 and 2 . These interactions account for 39.40% (Fig. 4 - 1 b) and 40.9%,(Fig. 4 - 2 b) respectively, of the total Hirshfeld surface in complexes 1 and 2 , respectively. The second biggest contribution to the overall Hirshfeld surface in complex 1 is made by Br∙∙∙H/H∙∙∙Br contacts (19.5%), followed by C∙∙∙H/H∙∙∙C (14.9% ) and H∙∙∙N/N∙∙∙H(11.3%) contacts respectively. For complex 2 , Br∙∙∙H/H∙∙∙Br( 20.6%) and C∙∙∙H/H∙∙∙C(16.5%) interactions provide considerably to the total Hirshfeld surface. The two distinct blue symmetric spikes (di + de ≅ 2.39 Å) in the fingerprint plot of complex 1 (Fig. 4 - 1 g) shows that 11.3% of the total Hirshfeld surface of the molecule making up H∙∙∙N/N∙∙∙H close contacts. On the other hand, for complex 2 , symmetric spikes (di + de ≅ 2.68 Å) on the fingerprint plot (Fig. 4 - 2 e) signifies that 7.8% of the total Hirshfeld surface of the molecule making up S···H/H∙∙∙S close contacts. For both complexes 1 and 2 , providing 14.9% (Fig. 4 - 1 d) and 16.5% (Fig. 4 - 2 c) of the total Hirshfeld surfaces, the C∙∙∙H/H∙∙∙C intermolecular contacts appear on the fingerprint plot as wing-like peripheral spikes at the top left and bottom right[ 65 ] of each plot, indicating C − H∙∙∙π interactions. The points on the surface surrounding the C − H donor are represented by the spike in the top left, while the points on the surface surrounding the π acceptor are represented by the spike in the bottom right[ 65 ]. The fingerprint plot of another Schiff base type complex likewise shows a characteristic for C∙∙∙H contacts[ 66 ]. Additionally, the C∙∙∙C contacts are seen for both the complexes 1 and 2 in the center of the fingerprint plot (di + de ≅ 3.3 Å, di + de ≅ 3.5 Å), contributing 4.7% and 4.8% of the total Hirshfeld surface indicating π∙∙∙π interactions. Figure 5 displays the comparative strength of all interactions in both complexes 1 and 2 . In order to better understand the single crystals mechanical durability, void analysis is carried out. It will be assumed that the molecules are tightly packed together if a unit cell has a minimal fraction of vacancies[ 67 ]. The crystal voids of complexes 1–2 are shown in Fig. 6 . This study suggests that the voids occupied 9.15% and 12.28% (Table 4) of the space in the crystal packing for both complexes 1 and 2 , respectively, indicating that the molecules can tolerate high levels of stress and are firmly bound to one another by non-covalent contacts. Density functional theory The main optimized ground state geometries are depicted in the Fig. 7 . For the complex 1 , HOMO and LUMO orbitals mainly originate from π and π* orbital contribution from the Mn-linked molecular assembly and with negligible electronic distribution on other molecular assembly part, thus validating weak fluorescent property of the complex. The energy difference (band gap) between HOMO and LUMO in the complex is calculated to be 0.01239 eV which is very low, revealing the shifting of the emission to longer wavelength region. So, theoretical studies well corroborated substantial changes in spectroscopic properties of the complex formation. FTIR spectra The FTIR spectra of complexes 1–2 are typical of distinct, strong bands caused by the azomethine (C = N) group at 1617 cm − 1 and 1615 cm − 1 respectively [ 52 ]. Because the pseudohalide group is present, Complexes 1–2 exhibit a strong and sharp band at 2058 cm − 1 and 2088 cm − 1 , respectively [ 53 ]. UV–Visible absorption spectra. UV-Visible absorption spectra of complexes 1 and 2 in methanol solution are shown in Fig. 8 a, which reflects the presence of six-coordinate octahedral geometry around each of the manganese (III) ions. The spectra exhibit several intense absorption bands in the range 225–280 nm, corresponding to π-π* transitions of the heterocyclic rings. Other bands at around 325 nm were assigned to the n-π* transitions of the non-bonding electrons present on the nitrogen of the azomethine group of the Schiff base. The higher intensity bands in 1 and 2 may be attributed to the LMCT or intra ligand n-π*/π-π* transitions in these complexes. The optical band gap energy of the complexes 1–2 were calculated by the Tauc’s equation[ 68 ] $${\left(\alpha h\upsilon \right)}^{2}= C(h\upsilon -{E}_{g})$$ Where α is the optical absorption coefficient, hυ is the photon energy, E g is the direct band gap and C is a constant. The corresponding Tauc’s plots are shown in the Fig. 8 b. The direct band gap of complexes 1–2 are extracted to be 4.87 eV and 4.67 eV, respectively and this measured value of the optical band gap signifies that the material belongs to the wide band gap semiconductor family. Interestingly, ~ 200meV band gap energy change is observed from 1 to 2 . Photoluminescence spectra The photoluminescence (PL) emission spectra of complexes 1–2 can reveal some vital information. The PL emission spectra of the complexes 1–2 were recorded at room temperature at an excitation wavelength of 300 nm, as shown in Fig. 8 c. The emission spectrum consists of some distinct and well intense peaks at 392 nm, 409 nm, 431 nm, and 460 nm which are attributed from the surface defects, oxygen vacancies, and photo induced charge carrier separation and recombination processes in the said materials[ 69 ], respectively. In case of 2 , the intensity of the PL emission spectrum is reduced by ~ 3 times with some distinct peaks at 389 nm, 431 nm, 470 nm, and 485 nm. Thermogravimetric analysis(TGA) The thermal analysis gives the information about nature of the material, phase transition, melting point, water of crystallization, and different stages of decomposition of the crystal system[ 70 ].Thermogravimetric analysis (TGA) of 1 and 2 were measured in the temperature range 30–570°C at a heating rate of 10°C min − 1 using Perkin Elmer thermal analyzer equipment (TGA 4000) in a N 2 atmosphere. The Thermogravimetric analysis (TGA) plot in change of weight percentage of the said crystal is illustrated in Fig. 9 a. The DGA profile indicates (Fig. 9 b) that there is no weight loss up to ~ 200°C and ~ 250°C for 1 and 2 , respectively. But in the temperature range, ~ 200–315°C and ~ 250–350°C a slow weight loss occurred in both complexes 1–2 respectively. Then up to 570°C, the weight loss was very slow. It implies that the material does not undergo any endothermic transition at ~ 100°C, which indicates the water of crystallization was not present in the said crystal. The first endothermic peak at 210°C and 260°C may be due to the decomposition and volatilization of the compound present in the crystals. The DGA analyses clearly reveal that the complexes 1–2 are thermally stable up to 210°C and 260°C respectively. Conclusion Two novel Manganese (III) Schiff base complexes, MnL 2 N 3 (1) and MnL 2 NCS (2), are successfully synthesized using a bidentate Schiff base ligand created from 5-Bromosalicylaldehyde and 2-thiopheneethylamine, incorporating azide ligand for 1 and thiocyanate ligand for 2 . The structures of both complexes have been justified through the application of single crystal X-ray diffraction and Hirshfeld surface analysis. Further characterizations of complexes include the use of spectroscopic techniques, Thermogravimetric analyses, and DFT for 1. The crystallographic data indicate that both the complexes form crystals in the orthorhombic space group P ca with manganese centres arranged in distorted octahedral geometry and coupled to one another by µ 1,3 bridging pseudohalide azide for 1 and thiocyanate for 2 anions. Several supramolecular interactions including weak hydrogen bonds, π···π, C–H···π interactions are suitably explained by Hirshfeld surface analysis. Voids parameter suggest that both molecules can tolerate high levels of stress. By using the Tauc method to estimate the direct optical band gap values of both complexes, it is revealed that these materials are classified as a member of the wide band gap semiconductor family. The DGA analyses clearly reveal that the complexes 1-2 are thermally stable up to 210 °C and 260 °C respectively. Hence, these studies reveal important details about the synthesis, structural characterizations, spectroscopic investigations, and thermal properties of 1D pseudohalide bridged manganese(III) complexes, significantly advancing the development of new coordination compounds. Declarations Author contribution statement 1. Uttam Mandal – Major contribution in synthesis part, Hirshfeld surface analysis 2. Corrado Rizzoli – Crystallography 3. Bikash Chakraborty – Spectral analysis 4. Srikanta Karmakar–TGA/DGA analysis 5. Swapnadip Roy– DFT 6. Santanu Mandal – Manuscript drafting 7. Debasis Bandyopadhyay – Overall supervision Declaration of competing interest In this paper, the authors declare that they have no known competing financial interests or personal relationships that may have affected their work. Acknowledgement Our thanks are extended to Dr. F B Mondal, Principal, Bankura Christian College for his constant encouragement and valuable suggestions in doing the work. 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J Mater Sci: Mater Electron 28:18787–18794. https://doi.org/10.1007/s10854-017-7828-z Appendix A. supplementary data CCDC 2104681 and 2104682 contains the supplementary crystallographic data for 1-2. These data can be obtained free of charge from The Cam-bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/da-ta_request/cif. Schemes Schemes 1-2 are available in the Supplementary Files section. Additional Declarations No competing interests reported. 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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-3281596","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":227911066,"identity":"858f7aa9-46ac-4311-99f3-ffa032fad198","order_by":0,"name":"Uttam Mandal","email":"","orcid":"","institution":"Bankura Sammilani College","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Uttam","middleName":"","lastName":"Mandal","suffix":""},{"id":227911067,"identity":"51fb2251-3ff6-4d86-aed9-3391bfb86c6e","order_by":1,"name":"Corrado Rizzoli","email":"","orcid":"","institution":"University of Parma","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Corrado","middleName":"","lastName":"Rizzoli","suffix":""},{"id":227911068,"identity":"f77a3b17-6282-4acd-b18f-257aa74b7169","order_by":2,"name":"Bikash Chakraborty","email":"","orcid":"","institution":"Bankura Christian College","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Bikash","middleName":"","lastName":"Chakraborty","suffix":""},{"id":227911069,"identity":"5ce3efb5-fd21-4805-98d4-1212db5e3270","order_by":3,"name":"Srikanta Karmakar","email":"","orcid":"","institution":"Calcutta University","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Srikanta","middleName":"","lastName":"Karmakar","suffix":""},{"id":227911070,"identity":"214a7fd3-8f2b-4ce7-a279-40e80d2a9043","order_by":4,"name":"Swapnadip Roy","email":"","orcid":"","institution":"Bankura Sammilani College","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Swapnadip","middleName":"","lastName":"Roy","suffix":""},{"id":227911071,"identity":"814cc51c-bcda-4bbf-8904-7464571ad9b0","order_by":5,"name":"Santanu Mandal","email":"","orcid":"","institution":"Bankura Christian College","correspondingAuthor":false,"submittingAuthor":false,"prefix":"","firstName":"Santanu","middleName":"","lastName":"Mandal","suffix":""},{"id":227911072,"identity":"9e2bae75-6aef-4a57-bdf4-94b6cdb0b61f","order_by":6,"name":"Debasis Bandyopadhyay","email":"data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAAZAAAAAyAQMAAABI0h/eAAAABlBMVEX///8AAABVwtN+AAAACXBIWXMAAA7EAAAOxAGVKw4bAAAA0ElEQVRIiWNgGAWjYDCCGzwg8gADA3sDAzNM8ABxWngOkKxFIgGhBS/gu9178MOPmjtyujPfGH4uqLBh4G9vYDxcgEeL5J1zyZI9x54Zm93OMZaecSaNQeLMAYbDM/BoMbiRY8bM2HA4cdvtHANp3rbDDAZAFx7mIUJL/babZ4x/k6QlwewGjxlxtkD9cthw25m0MmueM2k8EmcONuDVAg2xw/Jmxw9vvs1TYSPH3958+DM+LUiAwwBEAhUzNhCnAZhiHhCrchSMglEwCkYYAADL7VKaazDkawAAAABJRU5ErkJggg==","orcid":"","institution":"Bankura Christian College","correspondingAuthor":true,"submittingAuthor":false,"prefix":"","firstName":"Debasis","middleName":"","lastName":"Bandyopadhyay","suffix":""}],"badges":[],"createdAt":"2023-08-21 08:14:19","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-3281596/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-3281596/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s11243-023-00569-0","type":"published","date":"2024-01-27T15:19:52+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":42155744,"identity":"8f7df5ba-7f3e-4192-8542-9f44ba0d5b59","added_by":"auto","created_at":"2023-08-25 18:06:08","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":387305,"visible":true,"origin":"","legend":"\u003cp\u003eThe molecular structures of complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e with displacement ellipsoids drawn at the 50% probability level. Only the major components of the disordered thiophene rings are shown. Symmetry code: (i) 1/2-x, y, -1/2+z for \u003cstrong\u003e1\u003c/strong\u003eand (ii) 1/2-x, y, 1/2+z for \u003cstrong\u003e2\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/ef879f293b69214f20a82408.png"},{"id":42155940,"identity":"5b341f11-b0df-4d0c-af22-5007565571ab","added_by":"auto","created_at":"2023-08-25 18:14:08","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":664143,"visible":true,"origin":"","legend":"\u003cp\u003eCrystal packing diagrams of \u003cstrong\u003e1-2 \u003c/strong\u003eshowing the one-dimensional chains parallel to the \u003cem\u003ec\u003c/em\u003e axis in \u003cstrong\u003e1-2\u003c/strong\u003e. Interchain π....π stacking interactions are shown as dashed lines in \u003cstrong\u003e1-2\u003c/strong\u003e. Hydrogen atoms in \u003cstrong\u003e1-2\u003c/strong\u003e and the minor components of the disordered thiophene rings are omitted for clarity.\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/97dab1dbf5b20dd8bdeba469.png"},{"id":42154456,"identity":"7dbcbcf3-283f-4d98-8584-31b50b79bf79","added_by":"auto","created_at":"2023-08-25 17:50:08","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":239760,"visible":true,"origin":"","legend":"\u003cp\u003eHirshfeld surfaces of complexes \u003cstrong\u003e1-2\u003c/strong\u003e mapped over dnorm\u0026nbsp;(two distinct views),shape index and curvedness labelled as 1a,1b,1c and 2a,2b,2c respectively.\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/7727448c4c2a5c901591a4cc.png"},{"id":42156929,"identity":"eb6e48c7-96a3-45d4-84b8-b027fd329180","added_by":"auto","created_at":"2023-08-25 18:22:08","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":326096,"visible":true,"origin":"","legend":"\u003cp\u003e2D fingerprint plots of all interactions, represent the percentages of contacts contributed to the total Hirshfeld surface area of complexes\u003cstrong\u003e1-2\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/bbd759d09b9c8b57757b47ed.png"},{"id":42154447,"identity":"373b3f05-358c-4724-a666-70eac3679fb5","added_by":"auto","created_at":"2023-08-25 17:50:08","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":9688,"visible":true,"origin":"","legend":"\u003cp\u003eComparative study of intermolecular interaction to the Hirshfeld surface area of complexes \u003cstrong\u003e1-2\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/dd93c1869a010e873bcc558d.png"},{"id":42155218,"identity":"7aba1dec-4635-44d0-847e-a3c023745fd6","added_by":"auto","created_at":"2023-08-25 17:58:08","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":106539,"visible":true,"origin":"","legend":"\u003cp\u003eCrystal voids develop with iso-value of 0.002 au of complexes \u003cstrong\u003e1-2\u003c/strong\u003e.\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/922dedcbe45daec27c4f5ac4.png"},{"id":42155216,"identity":"c77fa101-b9cb-4457-aa54-93feacf3397d","added_by":"auto","created_at":"2023-08-25 17:58:08","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":108459,"visible":true,"origin":"","legend":"\u003cp\u003eOptimized structure ,HOMO and LUMO of the complex \u003cstrong\u003e1\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/3681087c4268bc54ba491a06.png"},{"id":42154457,"identity":"1adf2382-1c6a-4392-8bc3-27623f8adaf7","added_by":"auto","created_at":"2023-08-25 17:50:08","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":69229,"visible":true,"origin":"","legend":"\u003cp\u003e(a) UV-Vis. absorption spectra of complexes \u003cstrong\u003e1-2\u003c/strong\u003e; (b) Tauc’s plot of complexes \u003cstrong\u003e1-2\u003c/strong\u003e; (c). PL emission spectra of complexes \u003cstrong\u003e1-2.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"8.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/ad08142391599da68aca1e58.png"},{"id":42154454,"identity":"9c1ec83a-ad13-4ecd-8cf4-6de7891bfe26","added_by":"auto","created_at":"2023-08-25 17:50:08","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":45696,"visible":true,"origin":"","legend":"\u003cp\u003e(a) TGA plots of \u003cstrong\u003e1-2\u003c/strong\u003e; (b) DGA plots of \u003cstrong\u003e1-2.\u003c/strong\u003e\u003c/p\u003e","description":"","filename":"9.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/7aa3f666a393616b73e19cf0.png"},{"id":50314273,"identity":"9c188eb6-2d41-4d59-a3b4-7dd11f894986","added_by":"auto","created_at":"2024-01-29 15:29:58","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2279539,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/c516073f-8550-4c43-ab6a-6418efad1577.pdf"},{"id":42155213,"identity":"2d720a70-2caf-46b5-9eb3-72031769a0e1","added_by":"auto","created_at":"2023-08-25 17:58:08","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":16570,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme1.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/4adbd348a9503edea18a85a0.png"},{"id":42154448,"identity":"787f90dd-9ea2-4c79-abd7-70722016ba08","added_by":"auto","created_at":"2023-08-25 17:50:08","extension":"png","order_by":2,"title":"","display":"","copyAsset":false,"role":"supplement","size":50896,"visible":true,"origin":"","legend":"","description":"","filename":"Scheme2.png","url":"https://assets-eu.researchsquare.com/files/rs-3281596/v1/67ea504e62670da43f8d4e54.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Synthesis, crystal structure, and characterization of two new end-to-end 1D pseudohalide bridged manganese(III) complexes","fulltext":[{"header":"Introduction","content":"\u003cp\u003eSchiff base, a remarkable group of organic molecules, has appeared as a commonly used chelating ligand for the formation of transition metal complexes [\u003cspan additionalcitationids=\"CR2 CR3 CR4 CR5 CR6\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e]. For their fascinating properties in building competent catalysts[\u003cspan additionalcitationids=\"CR9 CR10\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e], promising magnetic materials[\u003cspan additionalcitationids=\"CR13 CR14\" citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e], vital pharmaceuticals[\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e], optoelectronic gadgets[\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e], bio-mimetic homolog[\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e] and so on, the newly produced Schiff bases and their complex compounds show considerable dedication to the research community[\u003cspan additionalcitationids=\"CR20 CR21 CR22 CR23\" citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e] .\u003c/p\u003e \u003cp\u003eThe coordination compound of manganese with a wide variety of Schiff base ligands has extensively been studied as a topic of great attention in bioinorganic chemistry[\u003cspan additionalcitationids=\"CR26 CR27\" citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e]. Redox enzymes containing manganese play important dynamic role in nature. Biological features of wide variety of Mn(III) complexes that can imitate the structural aspects of several metalloprotein, redox, and non-redox proteins [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e, \u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eMany of these compounds have also been found to have attractive catalytic [\u003cspan additionalcitationids=\"CR32\" citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e] and magnetic[\u003cspan additionalcitationids=\"CR35\" citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e] properties. The preparation and structural elucidation of such complexes has increased demand due to their biological relevance [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e], particularly in imitating the compound, such as, in photosystem II[\u003cspan additionalcitationids=\"CR39\" citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eThe pseudohalide anions (like azide and thiocyanate) can coordinate with metal ions as bridging linkers or as terminal ligands. They exhibit a wide range of coordination modes as bridging ligands. Among them, end-on(\u0026micro;\u003csub\u003e1,1\u003c/sub\u003e\u0026ndash;N\u003csub\u003e3\u003c/sub\u003e)[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e, \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e, \u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e] and end-to-end(\u0026micro;\u003csub\u003e1,3\u003c/sub\u003e\u0026ndash;N\u003csub\u003e3\u003c/sub\u003e)[\u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e, \u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]bridging is the most widespread (Scheme \u003cspan refid=\"Sch1\" class=\"InternalRef\"\u003e1\u003c/span\u003e). Although the coordination mode of an azido ligand to a particular metal ion is difficult to predict, it is believed that the steric and electronic properties of the co-ligands play a significant influence in this process.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003eThis paper describes the synthesis and characterization of two novel manganese (III) compounds with Schiff base salen-type ligands and pseudohalide as bridging ligands.\u003c/p\u003e"},{"header":"Experimental Section","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eMaterials and instruments\u003c/h2\u003e \u003cp\u003eAll compounds were reagent grade and were used as received from Sigma-Aldrich or Merck Companies without additional purification.\u003c/p\u003e \u003cp\u003e \u003cb\u003eCaution!!!\u003c/b\u003e Metal complexes with organic ligands in the presence of perchlorate and azide are potentially explosive, even though no difficulties were encountered in this study. Only a small amount of the material should be prepared, and it must be handled carefully.\u003c/p\u003e \u003cp\u003eThe UV\u0026ndash;Vis. absorption spectra of the prepared complexes were measured by UV\u0026ndash;Vis. Spectrophotometer (PerkinElmer model: lambda25) at a wavelength ranging from 200nm to 700nm. The\u003c/p\u003e \u003cp\u003ephotoluminescence emission spectra were measured by PL a spectrofluorimeter: Horiba Fluorolog 3\u0026ndash;22\u003c/p\u003e \u003cp\u003eluminescence spectrometer. Both the absorption and PL emission spectra were measured in the solution\u003c/p\u003e \u003cp\u003ephase. 10 mg of the prepared samples were mixed in 10 ml of methanol. Then the mixture was sonicated\u003c/p\u003e \u003cp\u003efor 30 min to obtain homogenous solution. The Fourier-transform infrared spectroscopy (FTIR) spectra were taken between 500 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 4000 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e using a spectrometer (PerkinElmer, spectrum 2). The thermogravimetric analysis (TGA) measurements were carried out using a TGA analyzer (Perkin-Elmer TGA 4000). Here, the samples were heated from room temperature to 750 \u003csup\u003e◦\u003c/sup\u003eC at a rate of 10 \u003csup\u003e◦\u003c/sup\u003eC min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, under an N\u003csub\u003e2\u003c/sub\u003e flux of 30 mL min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e.\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eSynthesis\u003c/h2\u003e \u003cdiv id=\"Sec5\" class=\"Section3\"\u003e \u003ch2\u003ePreparation of Ligand\u003c/h2\u003e \u003cp\u003e5-Bromosalicylaldehyde (201 mg) in a methanolic solution (20 mL) was added to a methanolic solution (20 mL) of 2-thiopheneethylamine (127 mg). The mixture was refluxed for 3 hours. The yellow solution was used to prepare the complex without isolating the ligand (HL).\u003c/p\u003e \u003c/div\u003e \u003c/div\u003e \u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003ePreparation of complexes1-2\u003c/h2\u003e \u003cp\u003eComplexes \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e2\u003c/b\u003e were prepared by mixing metal perchlorate, Schiff base ligand HL, and azide (for \u003cb\u003e1\u003c/b\u003e) or thiocyanate (for \u003cb\u003e2\u003c/b\u003e) in mixture of 60% acetonitrile and 40% ethanol for \u003cb\u003e1\u003c/b\u003e and acetonitrile for \u003cb\u003e2\u003c/b\u003e in a 1:1:1 molar ratio, followed by gradual evaporation.\u003c/p\u003e \u003cp\u003eMn (ClO\u003csub\u003e4\u003c/sub\u003e)\u003csub\u003e2\u003c/sub\u003e∙6H\u003csub\u003e2\u003c/sub\u003eO (360 mg, 1 mmol) dissolved in 10 ml of mixture of 60% acetonitrile and 40% ethanol was added dropwise to a solution of Schiff base ligand, HL (620mg, 2mmol) in a mixture of 60% acetonitrile and 40% ethanol at room temperature with steady stirring. Sodium azide (65 mg, 1 mmol) dissolved in a 4 mL mixture of 60% acetonitrile and 40% ethanol was progressively added to the resultant stirred solution. Stirring was continued for about 45 minutes, after which the solution was filtered and placed in a beaker open to the atmosphere for slow evaporation. Dark brown crystals of \u003cb\u003e1\u003c/b\u003e appeared after 5\u0026ndash;7 days. The crystals were collected after washing with a little mixture of 60% acetonitrile and 40% ethanol and drying.\u003c/p\u003e \u003cp\u003eThe preparation of complex 2 followed the same synthetic procedure as that of complex 1. For 2, acetonitrile and ammonium thiocyanate (76 mg, 1 mmol) respectively were used in place of mixture of 60% acetonitrile l and 40% ethanol and Sodium azide (65 mg, 1 mmol). Brown crystals were found after 5\u0026ndash;7 days.\u003c/p\u003e \u003cp\u003eFor compound \u003cb\u003e1\u003c/b\u003e: Yield 0.47 g (65%). Anal. Calc. C 43.65%, H 3.09%, N 9.79%. Found. C 43.67%, H 3.09%, N 9.81%. IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) 1617(s), 2058(s), 1301(s), 484(w). For compound \u003cb\u003e2\u003c/b\u003e: Yield 0.51 g (70%). Anal. Calc. C 44.33%, H 3.03%, N 5.74% Found: C 44.22%, H 3.01%, N 5.68%; IR (KBr pellet, cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e) 1615(s), 2088(s), 1294(s), 483(w).\u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003eX-ray crystallographic studies\u003c/h2\u003e \u003cp\u003eSingle crystal X-ray intensity data of \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e2\u003c/b\u003e were collected on a Bruker DUO VENTURE diffractometer equipped with graphite monochromated Mo K\u003csub\u003eα\u003c/sub\u003e radiation (λ\u0026thinsp;=\u0026thinsp;0.71073 \u0026Aring;) at 294(2) K. Data collection and reduction were carried out using the APEX3 and SAINT packages[\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e]. Multi-scan absorption correction using the SADABS software[\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e] was applied to the intensity data. The structures were solved by direct methods using SHELXT[\u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e] and refined with full-matrix least-squares on F\u003csup\u003e2\u003c/sup\u003e on all unique reflections using SHELXL-2019/3[\u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e46\u003c/span\u003e].\u003c/p\u003e \u003cp\u003eIn both complexes, the thiophene rings were found to be disordered over two orientations, sharing the C10/C12/C13 and C23/C25/C26 carbon atoms and rotated by 180\u0026deg; about the C9\u0026minus;C10 and C22\u0026minus;C23 bonds, with refined occupancy ratios of 0.760(7):0.240(0) and 0.627(6):0.373(6) for \u003cb\u003e1\u003c/b\u003e, and 0.530(5):0.470(5) and 0.828(6):0.172(6) for \u003cb\u003e2\u003c/b\u003e. During the refinement of the disordered rings, EXYZ and EADP restraints were applied.\u003c/p\u003e \u003cp\u003eAll hydrogen atoms were placed geometrically and refined using a riding atom approximation, with C\u0026thinsp;\u0026minus;\u0026thinsp;H\u0026thinsp;=\u0026thinsp;0.93\u0026ndash;0.97 \u0026Aring;, and with \u003cem\u003eU\u003c/em\u003e\u003csub\u003eiso\u003c/sub\u003e(H)\u0026thinsp;=\u0026thinsp;1.2\u003cem\u003eU\u003c/em\u003e\u003csub\u003eeq\u003c/sub\u003e(C). The crystal of both compounds were refined as a 2-component inversion twin using the matrix [-1 0 0, 0\u0026ndash;1 0, 0 0\u0026ndash;1] with a volume fraction for the two domains of 0.015(8):0.985(8) and 0.014(7):0.986(7) for \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e2\u003c/b\u003e, respectively. All figures were drawn using the ORTEP-3 [\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]and SCHAKAL-99 [\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e] programs.\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\u003eCrystallographic Data and Structural Refinement of Complexes 1and 2\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e\u0026nbsp;\u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003e\u003cem\u003e1\u003c/em\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cem\u003e2\u003c/em\u003e\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\u003e26\u003c/sub\u003eH\u003csub\u003e22\u003c/sub\u003eBr\u003csub\u003e2\u003c/sub\u003eMnN\u003csub\u003e5\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e2\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eC\u003csub\u003e27\u003c/sub\u003eH\u003csub\u003e22\u003c/sub\u003eBr\u003csub\u003e2\u003c/sub\u003eMnN\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS\u003csub\u003e3\u003c/sub\u003e\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\u003e715.36\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e731.41\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\u003eorthorhombic\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eorthorhombic\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\u003e\u003cem\u003ePca\u003c/em\u003e2\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e\u003cem\u003ePca\u003c/em\u003e2\u003csub\u003e1\u003c/sub\u003e\u003c/p\u003e \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\u003e16.5777(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e16.5423(4)\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\u003e13.1133(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e13.2615(3)\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\u003e12.7825(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e13.4661(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\alpha\\)\u003c/span\u003e\u003c/span\u003e\u003cem\u003e(˚)\u003c/em\u003e\u003c/p\u003e \u003cp\u003e\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\beta\\)\u003c/span\u003e\u003c/span\u003e\u003cem\u003e(˚)\u003c/em\u003e\u003c/p\u003e \u003cp\u003e\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\gamma\\)\u003c/span\u003e\u003c/span\u003e\u003cem\u003e(˚)\u003c/em\u003e\u003c/p\u003e \u003cp\u003e\u003cem\u003eV\u003c/em\u003e (\u0026Aring;\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90\u003c/p\u003e \u003cp\u003e90\u003c/p\u003e \u003cp\u003e90\u003c/p\u003e \u003cp\u003e2778.77(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e90\u003c/p\u003e \u003cp\u003e90\u003c/p\u003e \u003cp\u003e90\u003c/p\u003e \u003cp\u003e2954.14(12)\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\u003e4\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e4\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eD\u003c/em\u003e\u003csub\u003e\u003cem\u003ec\u003c/em\u003e\u003c/sub\u003e (g cm\u003csup\u003e\u0026minus;\u0026thinsp;3\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.710\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.645\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003e\u0026micro;\u003c/em\u003e (mm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e3.535\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e3.394\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\u003e1424\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1456\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eλ (Mo K\u003csub\u003eα\u003c/sub\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.71073\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.71073\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eθ range (\u0026deg;)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.98\u0026ndash;25.25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.97\u0026ndash;25.50\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eT\u003c/em\u003e (K)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e294(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e294(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eIndex ranges\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e-19\u0026thinsp;\u0026le;\u0026thinsp;h\u0026thinsp;\u0026le;\u0026thinsp;19\u003c/p\u003e \u003cp\u003e\u0026thinsp;\u0026minus;\u0026thinsp;15\u0026thinsp;\u0026le;\u0026thinsp;k\u0026thinsp;\u0026le;\u0026thinsp;15\u003c/p\u003e \u003cp\u003e\u0026ndash;15\u0026thinsp;\u0026le;\u0026thinsp;l\u0026thinsp;\u0026le;\u0026thinsp;15\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e-20\u0026thinsp;\u0026le;\u0026thinsp;h\u0026thinsp;\u0026le;\u0026thinsp;20\u003c/p\u003e \u003cp\u003e\u0026thinsp;\u0026minus;\u0026thinsp;16\u0026thinsp;\u0026le;\u0026thinsp;k\u0026thinsp;\u0026le;\u0026thinsp;16\u003c/p\u003e \u003cp\u003e\u0026ndash;16\u0026thinsp;\u0026le;\u0026thinsp;l\u0026thinsp;\u0026le;\u0026thinsp;16\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eReflections collected\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e71601\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e89268\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eUnique reflections\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e5004\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5407\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eReflections \u003cem\u003eI\u003c/em\u003e\u0026thinsp;\u0026gt;\u0026thinsp;2σ(\u003cem\u003eI\u003c/em\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e4839\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e5280\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e\u003csub\u003eint\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.038\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.031\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cem\u003eR\u003c/em\u003e (\u003cem\u003eI\u003c/em\u003e\u0026thinsp;\u0026gt;\u0026thinsp;2σ(\u003cem\u003eI\u003c/em\u003e) )\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.022\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.020\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003ew\u003cem\u003eR\u003c/em\u003e\u003csub\u003e\u003cem\u003e2\u003c/em\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.056\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.053\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eGoodness-of-fit (\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\u003e1.045\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e1.028\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eΔ\u003cem\u003eρ\u003c/em\u003emax/Δ\u003cem\u003eρ\u003c/em\u003emin (e \u0026Aring;\u003csup\u003e\u0026minus;3\u003c/sup\u003e)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e0.41 / -0.40\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003e0.37 / -0.31\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 distances (\u0026Aring;) and angles (\u0026deg;) of Complexes 1 and 2\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=\"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 \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c2\" namest=\"c1\"\u003e \u003cp\u003e\u003cem\u003e1\u003c/em\u003e\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colspan=\"2\" nameend=\"c4\" namest=\"c3\"\u003e \u003cp\u003e\u003cem\u003e2\u003c/em\u003e\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;O1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.869(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;O1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.856(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e1.861(2)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e1.866(2)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.052(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.047(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.041(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.054(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.234(3)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.183(3)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;N5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e2.356(4)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eMn1\u0026thinsp;\u0026minus;\u0026thinsp;S3\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e2.8022(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e179.82(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;O2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e172.31(11)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e89.97(10)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e89.60(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90.10(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e89.61(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90.03(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e95.54(12)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e88.84(14)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;S3\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e95.21(8)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e89.86(10)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N1\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90.13(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90.07(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90.28(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e90.00(12)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e92.21(11)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e91.12(14)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eO2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;S3\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e77.13(8)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e175.46(11)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N2\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e177.17(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e89.53(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e92.21(11)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e87.94(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;S3\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e93.26(8)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e95.01(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN1\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N3\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e90.57(11)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e87.52(13)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN2\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;S3\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e84.11(7)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eN3\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;N5\u003csup\u003ei\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003e177.24(15)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eN3\u0026thinsp;\u0026minus;\u0026thinsp;Mn1\u0026thinsp;\u0026minus;\u0026thinsp;S3\u003csup\u003eii\u003c/sup\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e168.61(10)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colspan=\"4\" nameend=\"c4\" namest=\"c1\"\u003e \u003cp\u003eSymmetry codes: (i) 0.5-x, y, -0.5\u0026thinsp;+\u0026thinsp;z; (ii) 0.5-x, y, 0.5\u0026thinsp;+\u0026thinsp;z.\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 \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eComputational details\u003c/h2\u003e \u003cp\u003eIn this study, Crystal Explore 21.5[\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e] software and the Crystallography information file of both complexes \u003cb\u003e1\u003c/b\u003e and \u003cb\u003e2\u003c/b\u003e were used to compute Hirshfeld surfaces (HS) and their corresponding 2D fingerprint plots (FP). These tools allowed the measurement and exploration of the many non-covalent intermolecular interactions in the crystal lattice. By using the normalized contact distance \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e, which took into account the separation between the surface spot and the nearest internal nucleus (d\u003csub\u003ei\u003c/sub\u003e) or external nucleus\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({(d}_{e}\\)\u003c/span\u003e\u003c/span\u003e), as well as the van der Waals radii of the atom (as shown by the Eq.\u0026nbsp;\u003cspan refid=\"Equ1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) facilitated the identification of the areas that were especially important for intermolecular interactions [\u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e].\u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$${d}_{norm}= \\frac{{d}_{e}-{r}_{i}^{vdw}}{{r}_{e}^{vdw}} + \\frac{{d}_{i}-{r}_{i}^{vdw}}{{r}_{i}^{vdw}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eWhen intermolecular interactions were, respectively, shorter or longer than van der Waals radii(vdW) of the atoms, the values of the \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003ewere negative or positive [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e]. A red-blue-white color combination was used to map the \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e values onto the Hirshfeld surface, where red regions represent closer interactions and a negative \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e value, blue regions represent longer contacts and a positive \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e value, and white regions represent contacts that were exactly separated by the van der Waals distance and had a zero \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e value. Hirshfeld surfaces were traced with \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e varying from \u0026minus;\u0026thinsp;0.656 (red) to 1.705 (blue) for \u003cb\u003e1\u003c/b\u003e and from \u0026minus;\u0026thinsp;0.518 (red) to 1.807 (blue) for \u003cb\u003e2\u003c/b\u003e, respectively and for shape index varying from \u0026minus;\u0026thinsp;0.997 (concave) to 0.999(convex) for \u003cb\u003e1\u003c/b\u003e and from \u0026minus;\u0026thinsp;0.993(concave) to 0.998(convex) for \u003cb\u003e2\u003c/b\u003e and for curvedness varying from \u0026minus;\u0026thinsp;3.838 (flat) to 0.358(singular) for \u003cb\u003e1\u003c/b\u003e and from \u0026minus;\u0026thinsp;3.558 (flat) to 0.409 (singular) for \u003cb\u003e2\u003c/b\u003e shows in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. Crystal voids were estimated utilizing Crystal Explorer 21.5[\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e] software. For Density Functional Theory (DFT) computation, we performed a ground state geometry optimization process for the complex \u003cb\u003e1\u003c/b\u003e based on X-ray diffraction data, and a fragment was chosen to obtain a perfect symmetry around the central metal ion with complete coordination as observed in the ligand cluster using B3LYP/6-31G(d,p) basis set in Gaussian 09 program [\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e, \u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e]. The DFT calculation was performed by taking pentadentate Mn system ligand clusters.\u003c/p\u003e \u003c/div\u003e"},{"header":"Results and Discussions","content":"\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\n \u003ch2\u003eSynthesis and Characterization\u003c/h2\u003e\n \u003cp\u003eSchiff base and pseudohalide ligand are reacted with \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({\\text{M}\\text{n}\\left(\\text{C}\\text{l}{\\text{O}}_{4}\\right)}_{2}\\bullet 6{\\text{H}}_{2}\\text{O}\\)\u003c/span\u003e\u003c/span\u003ein mixture of 60% acetonitrile and 40% ethanol for \u003cstrong\u003e1\u003c/strong\u003e and acetonitrile for \u003cstrong\u003e2\u003c/strong\u003e at room temperature to produce the Mn(III) complexes in a satisfactory yield (Scheme \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eBoth of these complexes form crystals in the orthorhombic space group \u003cem\u003eP\u003c/em\u003eca\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({2}_{1}\\)\u003c/span\u003e\u003c/span\u003e with manganese centres arranged in distorted octahedral geometry and coupled to one another by \u0026micro;\u003csub\u003e1,3\u003c/sub\u003e bridging pseudohalide (azide for \u003cstrong\u003e1\u003c/strong\u003e and thiocyanate for \u003cstrong\u003e2\u003c/strong\u003e) anions. The composition of complexes are predicted based on their X-ray crystallography, elemental analysis, Hirshfeld surface analysis and various spectroscopic results.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec11\" class=\"Section2\"\u003e\n \u003ch2\u003eDescription of the structures\u003c/h2\u003e\n \u003cp\u003eThe Mn(III) ions, octahedrally surrounded by four donor atoms (N2O2) from the Schiff base ligand constitute the equatorial plane and two (N, N) atoms from the azide or (N, S) atoms from thiocyanate ligands for compounds \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e, respectively. In contrast to the basal bond distances, which are within the range seen for structurally characterized manganese(III) complexes [\u003cspan class=\"CitationRef\"\u003e54\u003c/span\u003e\u0026ndash;\u003cspan class=\"CitationRef\"\u003e60\u003c/span\u003e], the axial bond distances are significantly larger (Table \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e). The elongation of axial bonds can be explained in terms of Jahn\u0026ndash;Teller distortion[\u003cspan class=\"CitationRef\"\u003e61\u003c/span\u003e].\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec12\" class=\"Section2\"\u003e\n \u003ch2\u003eHirshfeld surface analysis(HSA)\u003c/h2\u003e\n \u003cp\u003eHirshfeld surface analysis can offer a thorough view of the intermolecular interactions inherent in a molecule. Hirshfeld surface of complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e mapped over \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e(two distinct views), shape index and curvedness are shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e labelled as (1a,1b,1c) and (2a,2b,2c), respectively. The seven different red spots on the Hirshfeld surface area mapped over \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e of complex \u003cstrong\u003e1\u003c/strong\u003e (Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ea) confirmed the existence of C\u0026thinsp;\u0026minus;\u0026thinsp;H∙∙∙N/N∙∙∙H\u0026thinsp;\u0026minus;\u0026thinsp;C type weak hydrogen bonds, H⋯Br and N ⋯ Mn/Mn⋯N interactions. Likewise, analysis of \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\({d}_{norm}\\)\u003c/span\u003e\u003c/span\u003e Hirshfeld surface for complex \u003cstrong\u003e2\u003c/strong\u003e(Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ea) indicates that seven red spots signify the existence of C\u0026ndash;H⋯Br, C\u0026ndash;H⋯S type weak hydrogen bonds and Mn⋯S/S⋯Mn interactions. N⋯Mn/Mn⋯N interactions for \u003cstrong\u003e1\u003c/strong\u003e and Mn⋯S/S⋯M interactions for \u003cstrong\u003e2\u003c/strong\u003e are primarily responsible for creating the one-dimensional chain molecular structure[\u003cspan class=\"CitationRef\"\u003e62\u003c/span\u003e]. Orange and blue adjacent triangular regions (bow tie design) are visible in the shape index function for both complexes, which signifies the existence of \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\pi \\cdots \\pi\\)\u003c/span\u003e\u003c/span\u003estacking interactions. The detection of patches on flat surfaces on curvedness Hirshfeld Surface also confirms the existence of \u0026pi; ⋯\u0026pi; interactions. In Table\u0026nbsp;3, there are numerical values showing the molecule volume (V\u003csub\u003eH\u003c/sub\u003e), globularity (G), asphericity(Ω), and surface area (A\u003csub\u003eH\u003c/sub\u003e).Compared to complex \u003cstrong\u003e1\u003c/strong\u003e, complex \u003cstrong\u003e2\u003c/strong\u003e has more molecular volume, globularity, and asphericity but less surface area. Complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e have globularity values (0.675 and 0.711) that are less than unity, indicating the greatest deviance from a spherical surface[\u003cspan class=\"CitationRef\"\u003e63\u003c/span\u003e]. Asphericity (Ω) is a metric for molecular anisotropy, and value of complex \u003cstrong\u003e1 (\u003c/strong\u003e0.102) is relatively lower than that of the complex \u003cstrong\u003e2\u003c/strong\u003e (0.124), indicating a lesser departure from isotropy in the former[\u003cspan class=\"CitationRef\"\u003e64\u003c/span\u003e].\u003c/p\u003e\n \u003cp\u003e2D fingerprint plots of the both complexes are displayed in Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e. A plot of d\u003csub\u003ei\u003c/sub\u003e versus d\u003csub\u003ee\u003c/sub\u003e is a 2D fingerprint plot which recognizes the existence and amount of different type of intermolecular interactions. The H∙∙∙H intermolecular interactions play a significant role in the crystal packing of both complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e. These interactions account for 39.40% (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003eb) and 40.9%,(Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003eb) respectively, of the total Hirshfeld surface in complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e, respectively. The second biggest contribution to the overall Hirshfeld surface in complex \u003cstrong\u003e1\u003c/strong\u003e is made by Br∙∙∙H/H∙∙∙Br contacts (19.5%), followed by C∙∙∙H/H∙∙∙C (14.9% ) and H∙∙∙N/N∙∙∙H(11.3%) contacts respectively. For complex \u003cstrong\u003e2\u003c/strong\u003e, Br∙∙∙H/H∙∙∙Br( 20.6%) and C∙∙∙H/H∙∙∙C(16.5%) interactions provide considerably to the total Hirshfeld surface. The two distinct blue symmetric spikes (di\u0026thinsp;+\u0026thinsp;de \u0026cong; 2.39 \u0026Aring;) in the fingerprint plot of complex \u003cstrong\u003e1\u003c/strong\u003e(Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e -\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003eg) shows that 11.3% of the total Hirshfeld surface of the molecule making up H∙∙∙N/N∙∙∙H close contacts. On the other hand, for complex \u003cstrong\u003e2\u003c/strong\u003e, symmetric spikes (di\u0026thinsp;+\u0026thinsp;de \u0026cong; 2.68 \u0026Aring;) on the fingerprint plot (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ee) signifies that 7.8% of the total Hirshfeld surface of the molecule making up S\u0026middot;\u0026middot;\u0026middot;H/H∙∙∙S close contacts. For both complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e, providing 14.9% (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003ed) and 16.5% (Fig. \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e-\u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003ec) of the total Hirshfeld surfaces, the C∙∙∙H/H∙∙∙C intermolecular contacts appear on the fingerprint plot as wing-like peripheral spikes at the top left and bottom right[\u003cspan class=\"CitationRef\"\u003e65\u003c/span\u003e] of each plot, indicating C\u0026thinsp;\u0026minus;\u0026thinsp;H∙∙∙\u0026pi; interactions. The points on the surface surrounding the C\u0026thinsp;\u0026minus;\u0026thinsp;H donor are represented by the spike in the top left, while the points on the surface surrounding the \u0026pi; acceptor are represented by the spike in the bottom right[\u003cspan class=\"CitationRef\"\u003e65\u003c/span\u003e]. The fingerprint plot of another Schiff base type complex likewise shows a characteristic for C∙∙∙H contacts[\u003cspan class=\"CitationRef\"\u003e66\u003c/span\u003e]. Additionally, the C∙∙∙C contacts are seen for both the complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e in the center of the fingerprint plot (di\u0026thinsp;+\u0026thinsp;de \u0026cong; 3.3 \u0026Aring;, di\u0026thinsp;+\u0026thinsp;de \u0026cong; 3.5 \u0026Aring;), contributing 4.7% and 4.8% of the total Hirshfeld surface indicating \u0026pi;∙∙∙\u0026pi; interactions. Figure \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e displays the comparative strength of all interactions in both complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e.\u003c/p\u003e\n \u003cp\u003eIn order to better understand the single crystals mechanical durability, void analysis is carried out. It will be assumed that the molecules are tightly packed together if a unit cell has a minimal fraction of vacancies[\u003cspan class=\"CitationRef\"\u003e67\u003c/span\u003e]. The crystal voids of complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e are shown in Fig. \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e. This study suggests that the voids occupied 9.15% and 12.28% (Table 4) of the space in the crystal packing for both complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e, respectively, indicating that the molecules can tolerate high levels of stress and are firmly bound to one another by non-covalent contacts.\u003c/p\u003e\n \u003cp\u003e\u003cimg 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\"\u003e\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec13\" class=\"Section2\"\u003e\n \u003ch2\u003eDensity functional theory\u003c/h2\u003e\n \u003cp\u003eThe main optimized ground state geometries are depicted in the Fig. \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e. For the complex \u003cstrong\u003e1\u003c/strong\u003e, HOMO and LUMO orbitals mainly originate from \u0026pi; and \u0026pi;* orbital contribution from the Mn-linked molecular assembly and with negligible electronic distribution on other molecular assembly part, thus validating weak fluorescent property of the complex. The energy difference (band gap) between HOMO and LUMO in the complex is calculated to be \u003cstrong\u003e0.01239 eV\u003c/strong\u003e which is very low, revealing the shifting of the emission to longer wavelength region. So, theoretical studies well corroborated substantial changes in spectroscopic properties of the complex formation.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec14\" class=\"Section2\"\u003e\n \u003ch2\u003eFTIR spectra\u003c/h2\u003e\n \u003cp\u003eThe FTIR spectra of complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e are typical of distinct, strong bands caused by the azomethine (C\u0026thinsp;=\u0026thinsp;N) group at 1617 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1615 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e respectively [\u003cspan class=\"CitationRef\"\u003e52\u003c/span\u003e]. Because the pseudohalide group is present, Complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e exhibit a strong and sharp band at 2058 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 2088 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, respectively [\u003cspan class=\"CitationRef\"\u003e53\u003c/span\u003e].\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eUV\u0026ndash;Visible absorption spectra.\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003eUV-Visible absorption spectra of complexes \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e in methanol solution are shown in Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003ea, which reflects the presence of six-coordinate octahedral geometry around each of the manganese (III) ions. The spectra exhibit several intense absorption bands in the range 225\u0026ndash;280 nm, corresponding to \u0026pi;-\u0026pi;* transitions of the heterocyclic rings. Other bands at around 325 nm were assigned to the n-\u0026pi;* transitions of the non-bonding electrons present on the nitrogen of the azomethine group of the Schiff base. The higher intensity bands in \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e may be attributed to the LMCT or intra ligand n-\u0026pi;*/\u0026pi;-\u0026pi;* transitions in these complexes.\u003c/p\u003e\n \u003cp\u003eThe optical band gap energy of the complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e were calculated by the Tauc\u0026rsquo;s equation[\u003cspan class=\"CitationRef\"\u003e68\u003c/span\u003e]\u003c/p\u003e\n \u003cdiv id=\"Equa\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equa\" name=\"EquationSource\"\u003e$${\\left(\\alpha h\\upsilon \\right)}^{2}= C(h\\upsilon -{E}_{g})$$\u003c/div\u003e\n \u003c/div\u003e\n \u003cp\u003eWhere \u003cem\u003e\u0026alpha;\u003c/em\u003e is the optical absorption coefficient, \u003cem\u003eh\u0026upsilon;\u003c/em\u003e is the photon energy, \u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e is the direct band gap and C is a constant. The corresponding Tauc\u0026rsquo;s plots are shown in the Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003eb. The direct band gap of complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e are extracted to be 4.87 eV and 4.67 eV, respectively and this measured value of the optical band gap signifies that the material belongs to the wide band gap semiconductor family. Interestingly, ~\u0026thinsp;200meV band gap energy change is observed from \u003cstrong\u003e1\u003c/strong\u003e to \u003cstrong\u003e2\u003c/strong\u003e.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec15\" class=\"Section2\"\u003e\n \u003ch2\u003ePhotoluminescence spectra\u003c/h2\u003e\n \u003cp\u003eThe photoluminescence (PL) emission spectra of complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e can reveal some vital information. The PL emission spectra of the complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e were recorded at room temperature at an excitation wavelength of 300 nm, as shown in Fig. \u003cspan class=\"InternalRef\"\u003e8\u003c/span\u003ec. The emission spectrum consists of some distinct and well intense peaks at 392 nm, 409 nm, 431 nm, and 460 nm which are attributed from the surface defects, oxygen vacancies, and photo induced charge carrier separation and recombination processes in the said materials[\u003cspan class=\"CitationRef\"\u003e69\u003c/span\u003e], respectively. In case of \u003cstrong\u003e2\u003c/strong\u003e, the intensity of the PL emission spectrum is reduced by ~\u0026thinsp;3 times with some distinct peaks at 389 nm, 431 nm, 470 nm, and 485 nm.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec16\" class=\"Section2\"\u003e\n \u003ch2\u003eThermogravimetric analysis(TGA)\u003c/h2\u003e\n \u003cp\u003eThe thermal analysis gives the information about nature of the material, phase transition, melting point, water of crystallization, and different stages of decomposition of the crystal system[\u003cspan class=\"CitationRef\"\u003e70\u003c/span\u003e].Thermogravimetric analysis (TGA) of \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e were measured in the temperature range 30\u0026ndash;570\u0026deg;C at a heating rate of 10\u0026deg;C min\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e using Perkin Elmer thermal analyzer equipment (TGA 4000) in a N\u003csub\u003e2\u003c/sub\u003e atmosphere. The Thermogravimetric analysis (TGA) plot in change of weight percentage of the said crystal is illustrated in Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003ea. The DGA profile indicates (Fig. \u003cspan class=\"InternalRef\"\u003e9\u003c/span\u003eb) that there is no weight loss up to ~\u0026thinsp;200\u0026deg;C and ~\u0026thinsp;250\u0026deg;C for \u003cstrong\u003e1\u003c/strong\u003e and \u003cstrong\u003e2\u003c/strong\u003e, respectively. But in the temperature range, ~\u0026thinsp;200\u0026ndash;315\u0026deg;C and ~\u0026thinsp;250\u0026ndash;350\u0026deg;C a slow weight loss occurred in both complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e respectively. Then up to 570\u0026deg;C, the weight loss was very slow. It implies that the material does not undergo any endothermic transition at ~\u0026thinsp;100\u0026deg;C, which indicates the water of crystallization was not present in the said crystal. The first endothermic peak at 210\u0026deg;C and 260\u0026deg;C may be due to the decomposition and volatilization of the compound present in the crystals. The DGA analyses clearly reveal that the complexes \u003cstrong\u003e1\u0026ndash;2\u003c/strong\u003e are thermally stable up to 210\u0026deg;C and 260\u0026deg;C respectively.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eTwo novel Manganese (III) Schiff base complexes,\u0026nbsp;MnL\u003csub\u003e2\u003c/sub\u003eN\u003csub\u003e3\u003c/sub\u003e(1) and\u0026nbsp;MnL\u003csub\u003e2\u003c/sub\u003eNCS\u0026nbsp;(2), are successfully synthesized using a bidentate Schiff base ligand created from 5-Bromosalicylaldehyde and 2-thiopheneethylamine, incorporating azide ligand for \u003cstrong\u003e1\u003c/strong\u003e and thiocyanate ligand for \u003cstrong\u003e2\u003c/strong\u003e. The structures of both complexes have been justified through the application of single crystal X-ray diffraction and Hirshfeld surface analysis. Further characterizations of \u0026nbsp;complexes include the use of spectroscopic techniques,\u0026nbsp;Thermogravimetric analyses,\u0026nbsp;and DFT for 1. The crystallographic data indicate that\u0026nbsp;both \u0026nbsp;the complexes form crystals in the orthorhombic space group \u003cem\u003eP\u003c/em\u003eca\u0026nbsp;\u0026nbsp;with manganese centres arranged in distorted octahedral geometry and coupled to one another by \u0026micro;\u003csub\u003e1,3\u003c/sub\u003e bridging pseudohalide azide for\u003cstrong\u003e\u0026nbsp;1\u003c/strong\u003e and thiocyanate for\u0026nbsp;\u003cstrong\u003e2\u003c/strong\u003e anions.\u0026nbsp;Several supramolecular interactions including weak hydrogen bonds, \u0026pi;\u0026middot;\u0026middot;\u0026middot;\u0026pi;, C\u0026ndash;H\u0026middot;\u0026middot;\u0026middot;\u0026pi; interactions are suitably explained by Hirshfeld surface analysis. Voids parameter suggest that both molecules can tolerate high levels of stress. By using the Tauc method to estimate the direct optical band gap values of both complexes, it is revealed that these materials are classified as a member of the wide band gap semiconductor family.\u0026nbsp;\u0026nbsp;The DGA analyses clearly reveal that the complexes \u003cstrong\u003e1-2\u003c/strong\u003e are thermally stable up to 210 \u0026deg;C and 260 \u0026deg;C respectively. Hence, these studies reveal important details about the synthesis, structural characterizations, spectroscopic investigations, and thermal properties of 1D pseudohalide bridged manganese(III) complexes, significantly advancing the development of new coordination compounds.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003eAuthor contribution statement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003e1. Uttam Mandal – Major contribution in synthesis part, Hirshfeld surface analysis\u003c/p\u003e\n\u003cp\u003e2. \u0026nbsp;Corrado Rizzoli – Crystallography\u003c/p\u003e\n\u003cp\u003e3. Bikash Chakraborty – Spectral analysis\u003c/p\u003e\n\u003cp\u003e4. Srikanta Karmakar–TGA/DGA analysis\u003c/p\u003e\n\u003cp\u003e5. Swapnadip Roy–\u0026nbsp;DFT\u003c/p\u003e\n\u003cp\u003e6. Santanu Mandal – Manuscript drafting\u003c/p\u003e\n\u003cp\u003e7. Debasis Bandyopadhyay – Overall supervision\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eDeclaration of competing interest\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eIn this paper, the authors declare that they have no known competing financial interests or personal relationships that may have affected their work.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003eAcknowledgement\u003c/strong\u003e\u003c/p\u003e\n\u003cp\u003eOur thanks are extended to Dr. F B Mondal, Principal, Bankura Christian College for his constant encouragement and valuable suggestions in doing the work.\u003c/p\u003e\n\u003cp\u003eDr. Srikanta Karmakar is thankful to Dr. DS. 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J Mater Sci: Mater Electron 28:18787\u0026ndash;18794. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10854-017-7828-z\u003c/span\u003e\u003cspan address=\"10.1007/s10854-017-7828-z\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"},{"header":"Appendix A. supplementary data","content":"\u003cp\u003eCCDC 2104681 and 2104682 contains the supplementary crystallographic data for 1-2. These data\u003c/p\u003e\n\u003cp\u003e\u0026nbsp;can be obtained free of charge from The Cam-bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/da-ta_request/cif.\u003c/p\u003e"},{"header":"Schemes","content":"\u003cp\u003eSchemes 1-2 are available in the Supplementary Files section.\u003c/p\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":"transition-metal-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tmch","sideBox":"Learn more about [Transition Metal Chemistry](http://link.springer.com/journal/11243)","snPcode":"11243","submissionUrl":"https://submission.nature.com/new-submission/11243/3","title":"Transition Metal Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"Manganese (III), Schiff base complex, Crystal structure, thiocyanate, azide","lastPublishedDoi":"10.21203/rs.3.rs-3281596/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-3281596/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eTwo new Manganese (III) Schiff base complexes \u003cb\u003eMnL\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eN\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e (\u003cb\u003e1\u003c/b\u003e) and \u003cb\u003eMnL\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003cb\u003eNCS\u003c/b\u003e (\u003cb\u003e2\u003c/b\u003e) where HL is 4-bromo-2-[(\u003cem\u003eZ\u003c/em\u003e)-{[2-(thiophen-2-yl)ethyl]imino}methyl]phenol) were synthesized and characterized by UV\u0026ndash;Vis. absorption spectra, FT-IR, photoluminescence (PL) emission spectra, TGA Analyses, and single-crystal X-ray diffraction technique. Structural studies reveal that the metal sites in all complexes are six-coordinated by two phenoxy oxygen and two imine nitrogen atoms of two moles of Schiff base ligand, HL. The geometry around the metal center is twisted octahedral geometry with a MnN\u003csub\u003e4\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003e (for \u003cb\u003e1\u003c/b\u003e) and MnN\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS (for \u003cb\u003e2\u003c/b\u003e) chromophore. Hirshfeld surfaces associated with 2D fingerprint plots have been used to analyze intermolecular interactions in crystal packing. Computational study using Density Functional Theory (DFT) has been done (for \u003cb\u003e1\u003c/b\u003e) to elucidate the structural information and energy gap calculation between HOMO \u0026amp; LUMO. Crystal packing of both complexes shows the interchain π\u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(\\cdots\\)\u003c/span\u003e\u003c/span\u003eπ stacking interactions between one-dimensional chains.\u003c/p\u003e","manuscriptTitle":"Synthesis, crystal structure, and characterization of two new end-to-end 1D pseudohalide bridged manganese(III) complexes","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2023-08-25 17:50:03","doi":"10.21203/rs.3.rs-3281596/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Major revision","date":"2023-09-16T12:35:32+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2023-08-25T09:34:39+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"29a97a4e-47e4-4b86-b475-4e8def925bc6","date":"2023-08-24T23:57:59+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"03dc998a-8d40-4728-953f-6dd0059f805a","date":"2023-08-24T23:49:22+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"108fa3e4-9dde-475e-9f48-7950ddad3d8f","date":"2023-08-24T20:33:29+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"e5fc5ba5-6fa7-4eff-8423-02c9f8079fe0","date":"2023-08-22T22:38:26+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2023-08-21T23:42:09+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2023-08-21T23:30:03+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2023-08-21T15:28:17+00:00","index":"","fulltext":""},{"type":"submitted","content":"Transition Metal Chemistry","date":"2023-08-21T08:01:14+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"transition-metal-chemistry","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"tmch","sideBox":"Learn more about [Transition Metal Chemistry](http://link.springer.com/journal/11243)","snPcode":"11243","submissionUrl":"https://submission.nature.com/new-submission/11243/3","title":"Transition Metal Chemistry","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"em","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b9e7c6b3-87c6-4217-84c3-7c2dc1fba3a2","owner":[],"postedDate":"August 25th, 2023","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-01-29T15:28:10+00:00","versionOfRecord":{"articleIdentity":"rs-3281596","link":"https://doi.org/10.1007/s11243-023-00569-0","journal":{"identity":"transition-metal-chemistry","isVorOnly":false,"title":"Transition Metal Chemistry"},"publishedOn":"2024-01-27 15:19:52","publishedOnDateReadable":"January 27th, 2024"},"versionCreatedAt":"2023-08-25 17:50:03","video":"","vorDoi":"10.1007/s11243-023-00569-0","vorDoiUrl":"https://doi.org/10.1007/s11243-023-00569-0","workflowStages":[]},"version":"v1","identity":"rs-3281596","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-3281596","identity":"rs-3281596","version":["v1"]},"buildId":"WrCJVZZCHTDjtuVLN7oU0","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}