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), (C(18)H(15)S)(2)[MnCl(4)] (I), tri-phenyl-sulfonium tetra-chlorido-ferrate(III), (C(18)H(15)S)[FeCl(4)] (II), and bis-(tri-phenyl-sulfonium) tetra-chlorido-cobaltate(II), (C(18)H(15)S)(2)[CoCl(4)] (III), crystallize in the monoclinic space groups P2(1)/n [(I) and (III)] and P2(1)/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†à range and C-S-C angles observed at about 101 to 106°. The [MCl(4)] (n-) anions (M = Mn(2+), Fe(3+), Co(2+); n = 2,1,2) adopt slightly distorted tetra-hedral geometries, with M-Cl bond lengths in the 2.19-2.38†à 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 [MCl(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 inter-actions are observed.