Structural evidence of [Rh(Thio)6]3+ and [Rh(Thio)5Cl]2+ cations in three novel ionic systems based on Co(III) dioximates

Multicomponent mixed metal ionic-type dioximates, [Со(DH)2(Thio)2][Rh(Thio)6][BF4]4 (1), [Со(DH)2(Thio)2][Rh(Thio)6][TiF6]2·H2O (2) and [Со(NioxH)2(Thio)2]2[Rh(Thio)5Cl][TiF6]2·CH3OH·3H2O (3), where DH2 is dimethylglyoxime, NioxH2 is 1.2-cyclohexanedionedioxime, and Thio is thiourea, were synthesized and their structures were determined by an X-ray method. Compounds 1–3 consist of two different mononuclear coordination cations with cobalt(III) and rhodium(III) as octahedrally coordinated metal centers and fluorine-containing anions as counterions. In the studied systems, Rh(III) mostly binds Thio ligands instead of dioximes, while a typical bis-dioximate in trans geometry is formed by Co(III) with two Thio ligands placed in axial positions. A structural characterization of coordination cations [Rh(Thio)6]3+ and [Rh(Thio)5Cl]2+ is given for the first time. The interactions and arrangement of the components in crystals 1–3 are discussed.