Solvothermal synthesis, crystal structure and properties of [Mn(C 6H 18N 4)] 4Mn 2Sb 4S 12 containing the new hetero-metallic [Mn 2Sb 4S 12] core

Abstract

The novel thioantimonate(III) [Mn(C 6H 18N 4)] 4Mn 2Sb 4S 12 was synthesised under solvothermal conditions by reacting Mn, Sb and S in an aqueous solution of tren (=tris(2-aminoethyl)amine). In the structure MnS 4 tetrahedra and SbS 3 pyramids are linked via common corners and edges to form a new hetero-metallic [Mn 2Sb 4S 12] core. The [Mn(C 6H 18N 4)] 2+ cations are located at the periphery of the core and are bound to the [Mn 2Sb 4S 12] unit via two S atoms. Interesting features of the structure are two large angles around S atoms connecting neighboured MnS 4 tetrahedra. The competition between interatomic bonding interactions and steric requirements are responsible for this observation. The thermal decomposition proceeds in one step involving a complex redox reaction.