Solvothermal Syntheses and Characterization of Thiostannates [M(en)3]2Sn2S6 (M = Mn, Co, Zn), the Influence of Metal Ions on the Crystal Structure

Three new thiostannates [M(en)3]2Sn2S6 (en = ethylenediamine, M = Mn(1), Co(2) and Zn(3)) were synthesized by solvothermal method. The crystals were grown up in a Teflon‐lined steel autoclave at temperature about 180 °C. All the three compounds consist of discrete [Sn2S6]4— anions, which are dimer of two tetrahedral SnS4 sharing a common edge. The transition metal cations are six‐coordinated by three ethylenediamine molecules forming octahedral complex ions. Although the synthetic procedures, the mole ratio of the reactants and the solvent are essentially the same, the compound of MnII is quite different in structure from that of compounds of CoII and ZnII. Compound 1 crystallizes in monoclinic crystal system, C2/c, whereas compounds 2 and 3 crystallize in the orthorhombic crystal system, Pbca. Unlike compound 1, the [M(en)3]2+ cations in 2 and 3 are disordered. The difference of molecular packing between 1 and 2‐3 is considered due to the influence of the entities of the metal ions, such as radii and the coordination properties. The thermal chemical behaviors of the compounds 1‐3 were discussed and the results are also related to the property of the metal ions.