Using the solvothermal approach five new tin-sulfur compounds were synthesized. All compounds exhibit a direct covalent bond between the thiostannate unit and the charge compensating transition metal TM2+ ion, leading to the formation of discrete neutral molecules, chains or layered structures. In the structures, the [Sn2S6]4– anion is connected to the TM2+ cations in three different ways: (a) only two and opposite terminal S atoms are involved in bonding; (b) the four terminal S atoms connect two different complexes, and (c) the four terminal S atoms link four complexes. The compounds are: {[Ni(phen)2]2[Sn2S6]}·biph (1), {[Ni(phen)2]2[Sn2S6]}·phen·H2O (2), {[Fe(1,2-dach)2][Sn2S6]}n·2n1,2-dachH (3), {[Ni(cyclam)]2[Sn2S6]}n·2nH2O (4), and {[Mn(2,2′-bipy)2]2[Sn2S6]} (5). Compounds 1–3 were prepared from elements/chlorides, whereas for the preparation of compounds 4 and 5 a new synthesis strategy was developed using Na4SnS4·14H2O and TM2+ centered complexes as precursor. Under solvothermal conditions in situ condensation reaction of the [SnS4]4– anions leads to the formation of the [Sn2S6]4– moiety.