Syntheses and crystal structures of three tri-phenyl-sulfonium salts of manganese(II), iron(III) and cobalt(II).

Bis(tri-phenyl-sulfonium) tetra-chlorido-manganate(II), (C18H15S)2[MnCl4] (I), tri-phenyl-sulfonium tetra-chlorido-ferrate(III), (C18H15S)[FeCl4] (II), and bis-(tri-phenyl-sulfonium) tetra-chlorido-cobaltate(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 tri-phenyl-sulfonium (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 tetra-hedral 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 inter-actions 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 inter-actions are observed.