Crystal structures of three salts of the triphenylsulfonium ion

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 group P21/n, while [TPS][ClO4] (II) crystallizes in P21. 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.