An unusual Co2-containing anion: synthesis and structure of [(OxS)Ca·4HMPA]+·[(OxS)Co·µ-(OxS)3·CoCl]–[OxS–= C6H4O·(CS)N–; HMPA = OP(NMe2)3]

Abstract

Solid CoCl₂ dissolves in a toluene solution of (OxS)₂ Ca·2HMPA to give [(OxS)Ca·4HMPA]⁺·[(OxS)Co·µ-(OxS)₃·CoCl]^–, 1, the anion structure consists of two Co₂⁺ centres linked by three symmetrically bridging OxS^– ligands such that one Co²⁺(bonded through S to a terminal OxS^–) has a tetrahedral coordination sphere of four S atoms whilst the other (bonded to a terminal Cl^–) has a tetrahedral coordination sphere of three N and one Cl atoms.