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Bis(triphenylsulfonium) tetrachloridozinc(II), (C₁₈H₁₅S)₂[ZnCl₄] (I), bis(triphenylsulfonium) tetrachloridocadmium(II), (C₁₈H₁₅S)₂[CdCl₄] (II), and bis(triphenylsulfonium) tetrachloridomercury(II) methanol monosolvate, (C₁₈H₁₅S)₂[HgCl₄]·CH₃OH (III), each crystallize in the monoclinic space groupP2₁/n. In all three structures, there are two crystallographically independent triphenylsulfonium (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 [MCl₄]^2–anions (M= Zn²⁺, Cd²⁺, Hg²⁺) are tetrahedral; their M—Cl bond lengths systematically increase from Zn²⁺to Hg²⁺, 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...Minteractions anchor each [MCl₄]^2–anion to two surrounding TPS cations. Weak C—H...Cl hydrogen bonds, as well as inversion-centered π–π stacking, generate layers in (I) and (II) and dimeric [(TPS)₂–HgCl₄]₂assemblies in (III). 

The reactions of triphenylsulfonium chloride ([TPS][Cl]) with various acids in methanol yield the corresponding salts triphenylsulfonium triiodide, C₁₈H₁₅S⁺·I₃⁻or [TPS][I₃] (I), triphenylsulfonium perchlorate, C₁₈H₁₅S⁺·ClO₄⁻or [TPS][ClO₄] (II), and triphenylsulfonium hexafluorophosphate, C₁₈H₁₅S⁺·PF₆⁻or [TPS][PF₆] (III), as crystalline products. These crystals were structurally characterized by single-crystal X-ray diffraction. In all three compounds, the sulfur atom in the triphenylsulfonium cation adopts a distorted trigonal–pyramidal geometry. [TPS][I₃] (I) and [TPS][PF₆](III) both crystallize in the space groupP2₁/n, while [TPS][ClO₄] (II) crystallizes inP2₁. The S—C bond lengths are comparable across the three salts, and the S—C—S bond angles are consistently between 102 and 106°. Hirshfeld surface analyses reveal that each structure is dominated by hydrogen-based intermolecular contacts, supplemented by anion-specific interactions such as I...H in (I), O...H in (II), and F...H in (III). These contacts organize the ions into mono-periodic ribbon- or chain-like arrangements. No significant π–π stacking is observed.