The synthesis and characterisation of four new antimony sulphides incorporating transition-metal complexes

Four new antimony sulphides, [T(dien)₂]Sb₆S₁₀·xH₂O [T=Ni (1), Co (2)x≈0.45], [Co(en)₃]Sb₈S₁₃(3) and [Ni(en)₃]Sb₁₂S₁₉(4), have been synthesised under solvothermal conditions. In compounds (1) (3), Sb₁₂S₂₂^8- secondary building units are connected to form layered structures. In (1) and (2), Sb₆S₁₀^2- layers containing Sb₁₆S₁₆ heterorings are separated by [T(dien]₂]²⁺ cations, whilst in (3), Sb₈S₁₃^2- layers contain [Co(en)₃]²⁺ cations within large Sb₂₂S₂₂ pores. Compound (4) adopts a three-dimensional structure in which [Ni(en)₃]²⁺ cations lie within ca. 5 Å wide channels.