Syntheses and crystal structures of three tri­phenyl­sulfonium salts of manganese(II), iron(III) and cobalt(II)

Abstract

The crystal structures of three salts of the tri­phenyl­sulfonium cation, C₁₈H₁₅S⁺, namely bis­(tri­phenyl­sulfonium) tetra­chlorido­manganate(II), tri­phenyl­sulfonium tetra­chlorido­ferrate(III) and bis­(tri­phenyl­sulfonium) tetra­chlorido­cobaltate(II) are reported.

Bis(tri­phenyl­sulfonium) tetra­chlorido­manganate(II), (C₁₈H₁₅S)₂[MnCl₄] (I), tri­phenyl­sulfonium tetra­chlorido­ferrate(III), (C₁₈H₁₅S)[FeCl₄] (II), and bis­(tri­phenyl­sulfonium) tetra­chlorido­cobaltate(II), (C₁₈H₁₅S)₂[CoCl₄] (III), crystallize in the monoclinic space groups P2₁/n [(I) and (III)] and P2₁/c [(II)]. Compounds (I) and (III) each contain two crystallographically independent tri­phenyl­sulfonium (TPS⁺) cations in the asymmetric unit, whereas (II) has one. In all three compounds, the sulfonium centers adopt distorted trigonal–pyramidal geometries, with S—C bond lengths falling roughly in the 1.78–1.79 Å range and C—S—C angles observed at about 101 to 106°. The [MCl₄]ⁿ⁻ anions (M = Mn²⁺, Fe³⁺, Co²⁺; n = 2,1,2) adopt slightly distorted tetra­hedral geometries, with M—Cl bond lengths in the 2.19–2.38 Å range and Cl—M—Cl angles of approximately 104–113°. Hirshfeld surface analyses shows that H⋯H and H⋯C contacts dominate the TPS⁺ cation environments, whereas H⋯Cl and short M—S inter­actions link each [MCl₄]ⁿ⁻ anion to the surrounding cations. In (I) and (III), inversion-centered π–π stacking further consolidates the crystal packing, while in (II) no π–π inter­actions are observed.