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 Co(III)-Rh(III) ionic-type systems based on dioximates [Со(DH)2(Thio)2] or [Со(NioxH)2(Thio)2]. ► Compounds comprise novel coordination cations [Rh(Thio)6]3+ or [Rh(Thio)5Cl]2+ and [TiF6]2 or [BF4] as counteranions. ► A structural characterization of coordination cations [Rh(Thio)6]3+ and [Rh(Thio)5Cl]2+ is given for the first time. ► Cations and anions interact in the crystal via H-bonds, thus fluorine-containing anions are in the outer coordination sphere.