Synthesis and crystallographic characterization of a mononuclear cobalt(III) complex possessing both thiol­ate and thio­ether donors: reactivity of an thiol­ate-bridged penta­nuclear Co(2)Ag(3) complex with iodo­methane

Treatment of an S-bridged penta­nuclear Ag(I) (3)Co(III) (2) complex, [Ag(3){Co(L)}(2)](3+) [L (3–) = N(CH(2)NHCH(2)CH(2)S(−))(3)], in which two tris­(thiol­ate)-type mononuclear Co(III) units ([Co(L)]) are bridged by three Ag(I) ions through S atoms, with iodo­methane (CH(3)I) gave a new Co(III) mononuclear complex, [Co(LMe(2))](2+) [LMe(2) (−) = N(CH(2)NHCH(2)CH(2)S(−))(CH(2)NHCH(2)CH(2)SCH(3))(2)], systematic name: {2-[(bis{[2-(methylsulfanyl)ethyl]aminomethyl}aminomethyl)amino]ethanethiolato}cobalt(III) bis(hexafluoridophosphate). This cationic complex was crystallized with PF(6) (−) anions to form the title compound, [Co(LMe(2))](PF(6))(2). In the [Co(LMe(2))](2+) cation, two of three thiol­ate groups in [Co(L)] are methyl­ated while one thiol­ate group remains unreacted. Although a total of eight stereoisomers are possible for [Co(LMe(2))](2+), only a pair of enanti­omers {Λ(RR)- and Δ(SS)-[Co(LMe(2))](2+)} are selectively formed. In the crystal, the complex cations and the PF­(6) (−) anions are connected through weak N—H⋯F, C—H⋯F and C—H⋯S hydrogen bonds into a three-dimensional structure. Two F atoms in one PF(6) anion are disordered over two sets of sites with refined occupancies of 0.61 (4) and 0.39 (4) and two F atoms in the other PF(6) (−) anion are disordered over two sets of sites with occupancies of 0.5.