The four new thiostannates [Ni(en)3]2Sn2S6 (1) (en = ethylenediamine), [Ni(dap)3]2Sn2S6 · 2 H2O (2) (dap = 1, 2‐diaminopropane), [Co(tren)]2Sn2S6 (3) and [Ni(tren)]2Sn2S6 (4) (tren = tris(2‐aminoethyl)amine) were prepared under solvothermal conditions. In all compounds [Sn2S6]4— anions are observed as the common structural motif. This anion is composed of two SnS4 tetrahedra sharing a common edge. In compounds 1 and 2 the transition metal cations are coordinated each by three amine ligands and therefore solvent separated complex cations as well as discrete [Sn2S6]4— anions are found. In compounds 3 and 4 the coordination around the transition metal ions cannot be completed by the organic ligands and the [Sn2S6]4— anions are connected to the transition metal cations via terminal S atoms. In both compounds the [Sn2S6]4— anion acts as a bidentate ligand connecting two transition metal cations by terminal S atoms. The Co2+ cations in compound 3 are in a fivefold environment of one tetradentate tren ligand and one S atom forming discrete[Co(tren)]2Sn2S6 units. In compound 4 the Ni2+ ions are in a sixfold environment of one tetradentate tren ligand and two S atoms of two symmetry related [Sn2S6]4— anions. This connection mode leads to formation of “zig‐zag‐like” Ni—Sn2S6 chains which are directed along the crystallographic c‐axis. The spectroscopic properties of compounds 1 to 3 were investigated using Raman spectroscopy. Differences in the spectra of 1 and 2 compared to 3 are observed which are caused by the covalent bonding between the Co2+ ions and the Sn2S64— anions in 3.

Key indicatorsSingle-crystal X-ray study T = 293 K Mean '(C±C) = 0.004 A Ê R factor = 0.019 wR factor = 0.054 Data-to-parameter ratio = 28.0For details of how these key indicators were automatically derived from the article, see

In the crystal structure of the title compound, [Ni(2)(C(4)H(4)O(6))(2)(H(2)O)(2)].3H(2)O, two nickel cations, two tartrate anions and two water molecules form the dimeric complex. Each nickel cation is in a distorted octahedral environment composed of four O atoms of two crystallographically independent tartrate anions, one water molecule and one O atom of a symmetry-equivalent tartrate anion. The asymmetric unit contains three additional water molecules which are connected via hydrogen bonding.