Crystal structure and optoelectronic properties of a supramolecular chlorobismuthate salt templated with 4-pyridiniumthioamide

The organic-inorganic hybrid material with formula (C6H7N2S)2[BiCl6].H2O is synthesized at room temperature by slow evaporation method. It crystallizes in the monoclinic symmetry, space group P21/m, with the following parameters a = 8.2832 (9) Å, b = 16.1576 (16)Å, c = 8.9272 (9)Å, β= 108.571 (6)° Z = 2 and V = 1132.6 (2)Å3. However, the supramolecular structure is built from the mineral entities: hexachlorobismuthate (III) complex [BiCl6]3−, chloride atom anion and free water molecule, which are linked together and to the organic protonated 4-pyridinethioamide molecule by hydrogen bonds only, to form a zero dimensional network. The Hirshfeld analysis results show that in all potential molecular contacts, the H…Cl/Cl…H constitutes the most important interaction in the crystal (44.2 %). Vibrational spectroscopy analysis confirm the existence of vibrational modes that correspond to the protonated 4-pyridinethioamide molecule as an organic part in the material. Computational details of the molecular geometry optimization and calculation by DFT method show that the energy gap ∆ELUMO–HOMO is found to be 1.87 eV into the hybrid compound. Finally, photoluminescence measurement indicates that the synthesized material manifests luminescence property in its solid state.