Abstract The new organic–inorganic hybrid zero-dimensional bismuth-chloride based compound: (C3H6N3S2)3BiCl6, was synthesized by slow evaporation at room temperature. Single-crystal X-ray diffraction analysis indicates that the compound belongs to the triclinic crystal system with the centrosymmetric space group P-1. The asymmetric unit contains one octahedral geometry of [BiCl6]3- and three protonated cations (C3H6N3S2)+. In the crystal structure, the isolated [BiCl6]3- anions are linked to organic cations via N–H⋯Cl and C–H⋯Cl hydrogen bonds. Vibrational assignments of (C3H6N3S2)3BiCl6 are interpreted by FT-IR and Raman spectroscopic studies. The optimized molecular structure and vibrational frequencies were calculated by the Density Functional Theory (DFT) method using the B3LYP function with the LanL2DZ basis set. It shows a good agreement between the calculated and the experimental vibrational frequencies. The crystal packing is stabilized by N/C–H⋯Cl interactions whereas the van der Waals contacts play a key role in the consolidation of the 3D packing as verified by Hirshfeld surface analysis in combination with 2D fingerprint plots. The two-dimensional fingerprint plots reveal that the structure is dominated by Cl⋯H/H⋯Cl, H⋯N/N⋯H and H⋯H contacts. The crystal exhibits the thermal stability up to 270 °C using thermal analysis. The proton affinity (PA) values of the protonated AMT have been theoretically estimated on the basis of DFT calculations. The fluorescence measurements show two blue peaks which are attributed to band to band and excitonic emissions within the chlorobismuthate octahedron.

中文翻译：

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新型 Bi(III) 卤化物配合物 (tris(2-Amino-5-(methylthio)-1,3,4-thiadiazol-3-ium) hexachlorobismuthate(III)) 的合成、晶体结构、振动和光学性质：[C3H6N3S2 ]3BiCl6

摘要 在室温下缓慢蒸发合成了一种新的有机-无机杂化零维氯化铋基化合物：(C3H6N3S2)3BiCl6。单晶X射线衍射分析表明该化合物属于三斜晶系，具有中心对称空间群P-1。不对称单元包含一个八面体几何结构的 [BiCl6]3- 和三个质子化阳离子 (C3H6N3S2)+。在晶体结构中，孤立的 [BiCl6]3- 阴离子通过 N–H⋯Cl 和 C–H⋯Cl 氢键与有机阳离子相连。(C3H6N3S2)3BiCl6 的振动归属由 FT-IR 和拉曼光谱研究解释。优化的分子结构和振动频率是通过密度泛函理论 (DFT) 方法计算的，使用 B3LYP 函数和 LanL2DZ 基组。它显示了计算和实验振动频率之间的良好一致性。晶体堆积由 N/C–H⋯Cl 相互作用稳定，而范德华接触在 3D 堆积的固结中起关键作用，如 Hirshfeld 表面分析结合 2D 指纹图所证实的。二维指纹图显示结构以 Cl⋯H/H⋯Cl、H⋯N/N⋯H 和 H⋯H 接触为主。使用热分析，晶体表现出高达 270 °C 的热稳定性。质子化 AMT 的质子亲和力 (PA) 值已在 DFT 计算的基础上进行了理论上的估计。荧光测量显示两个蓝色峰，它们归因于氯铋八面体内的带间和激子发射。