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Two thiostannates [Ni(en)3]2Sn2S6 (1) (en = ethylenediamine) and [Ni(dien)2]2Sn2S6 (2) (dien = diethylenetriamine) were prepared by the reaction of SnCl4 · 5H2O, NiCl2 · 6H2O and S8 in a molar ratio of Sn/Ni/S =1:1:4 (or SnCl4:NiCl2:S8 = 1:1:0.5) under solvothermal conditions. Both compounds are composed of the discrete [Sn2S6]4− anion. The coordinated cations [Ni(en)3]2+ and [Ni(dien)2]2+ act as structure directing agents which lead to different packing of the [Sn2S6]4− anions. Compounds 1 and 2 decompose at 291 and 310 °C, respectively, and both of them lose all of their organic ligands in one step under a nitrogen stream. The hydrogen bonds are considered to be one of the important reasons for their difference in decomposition temperature. [Copyright &y& Elsevier]