Self-assembled tin(IV) organic-inorganic hybrids: Synthesis, spectral, structural, and Hirshfeld surface analysis of bis(thiomorpholinium) hexahalostannate(IV)

• Published in: Journal of molecular structure 2024-12, Vol.1318, p.139382, Article 139382
• Main Authors: Sivaprakasam, A., Normamatov, A.S., Guganathan, L., Ibragimov, A.B., Suppuraj, P., Syed, Asad, Bahkali, Ali H., Wong, L.S., Mohammad, M.R., Balakrishnan, C.
• Format: Article
• Language: English
• Subjects: Band gap; BVS; Crystal structures; Hirshfeld surface; Thiomorpholinium
• ISSN: 0022-2860
• DOI: 10.1016/j.molstruc.2024.139382

•Self-assembly of less toxic Tin(IV)–thiomorpholinium hybrids harvests at room temperature.•The BVS values for (C4H10NS)2SnCl6.H2O and (C4H10NS)2SnBr6 are 4.01 and 3.94, respectively, confirming the formal oxidation state of tin as a quadrivalent.•The effective coordination number values suggest that both compounds exhibit near-perfect octahedral geometry.•The energy gap for the bromo hybrid is 3.00 eV, while that of the chloro hybrid is 3.91 eV.•The intermolecular interactions present in compounds were elucidated through the analysis of 3D Hirshfeld surfaces and 2D fingerprint plots. At room temperature, organic-inorganic hybrids, including bis(thiomorpholinium) hexachlorostannate(IV) hydrate (1) and bis(thiomorpholinium) hexabromostannate(IV) (2), were synthesized from thiomorpholinium chloride/bromide. The hybrids underwent characterization using, IR, elemental, NMR, TGA, DRS and PL spectroscopy, along with single-crystal X-ray diffraction (SCXRD). SCXRD confirms compounds are crystallized in a monoclinic system exhibiting centrosymmetric space groups (C2/candP21/c for (1) and (2)). The SCXRD structures of the hybrids unveiled significant H-bonded interactions between the thiomorpholinium cation and the SnCl62-/SnBr62- anions. At room temperature, optical absorption measurements revealed band gaps of 3.91 eV for (1) and 3.00 eV for (2).TGA confirmed the proposed formulas of the compounds.BVS calculations conducted on SnCl62- and SnBr62- anions yielded values of 4.01 and 3.94, respectively. Fingerprint plots were employed to identify and quantify the proportion of hydrogen bonding interactions. [Display omitted]