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

Bis(triphenylsulfonium) tetrachloridomanganate(II), (C 18 H 15 S) 2 [MnCl 4 ] ( I ), triphenylsulfonium tetrachloridoferrate(III), (C 18 H 15 S)[FeCl 4 ] ( II ), and bis(triphenylsulfonium) tetrachloridocobaltate(II), (C 18 H 15 S) 2 [CoCl 4 ] ( III ), crystallize in the monoclinic space groups P 2 1 / n [( I ) and ( III )] and P 2 1 / 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 [ M Cl 4 ] n − anions ( M = Mn 2+ , Fe 3+ , Co 2+ ; 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 [ M Cl 4 ] 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.