Artis Rylan, Heyward Elizabeth, Reyes Naomi, Van Ostenbridge Kaitlyn, Lynch Will E, Padgett Clifford W
Department of Biochemistry Chemistry and Physics Georgia Southern University, Armstrong Campus 11935 Abercorn Street Savannah GA 31419 USA.
Acta Crystallogr E Crystallogr Commun. 2025 Mar 27;81(Pt 4):358-363. doi: 10.1107/S2056989025002245. eCollection 2025 Apr 1.
Bis(tri-phenyl-sulfonium) tetra-chlorido-zinc(II), (CHS)[ZnCl] (), bis-(tri-phenyl-sulfonium) tetra-chlorido-cadmium(II), (CHS)[CdCl] (), and bis-(tri-phenyl-sulfonium) tetra-chlorido-mercury(II) methanol monosolvate, (CHS)[HgCl]·CHOH (), each crystallize in the monoclinic space group 2/. In all three structures, there are two crystallographically independent tri-phenyl-sulfonium (TPS) cations per asymmetric unit, each adopting a distorted trigonal-pyramidal geometry about the S atom (S-C bond lengths in the 1.77-1.80 Å range and C-S-C angles of 100-107°). The [Cl] anions ( = Zn, Cd, Hg) are tetra-hedral; their M-Cl bond lengths systematically increase from Zn to Hg, consistent with the larger ionic radius of the heavier metal. Hirshfeld surface analyses show that H⋯H and H⋯C contacts dominate the TPS cation environments, whereas H⋯Cl and S⋯ inter-actions anchor each [Cl] anion to two surrounding TPS cations. Weak C-H⋯Cl hydrogen bonds, as well as inversion-centered π-π stacking, generate layers in () and () and dimeric [(TPS)-HgCl] assemblies in ().
二（三苯基锍）四氯合锌（II），(C₆H₅)₃S⁺[ZnCl₄]²⁻ ，二（三苯基锍）四氯合镉（II），(C₆H₅)₃S⁺[CdCl₄]²⁻ ，以及二（三苯基锍）四氯合汞（II）甲醇单溶剂合物，(C₆H₅)₃S⁺[HgCl₄]²⁻·CH₃OH ，均以单斜空间群 C2/c 结晶。在所有这三种结构中，每个不对称单元中有两个晶体学独立的三苯基锍（TPS）阳离子，每个阳离子围绕 S 原子采用扭曲的三角锥几何构型（S - C 键长在 1.77 - 1.80 Å 范围内，C - S - C 角度为 100 - 107°）。[Cl₄]²⁻ 阴离子（M = Zn、Cd、Hg）为四面体构型；它们的 M - Cl 键长从 Zn 到 Hg 系统性增加，这与较重金属较大的离子半径一致。 Hirshfeld 表面分析表明，H⋯H 和 H⋯C 接触在 TPS 阳离子环境中占主导，而 H⋯Cl 和 S⋯相互作用将每个[Cl₄]²⁻ 阴离子锚定到两个周围的 TPS 阳离子上。弱 C - H⋯Cl 氢键以及以反演中心的 π - π 堆积，在（化合物 1）和（化合物 2）中形成层状结构，在（化合物 3）中形成二聚体[(TPS)₂ - HgCl₄]组装体。
