Solvothermal Syntheses and Characterization of New Transition Metal Chalcogenidogermanates [{Co(tepa)} 2 (μ‐Ge 2 S 6 )] and [{M(tepa)} 2 (μ‐Ge 2 Se 6 )] (M = Mn, Fe) (tepa = Tetraethylenepentamine)

New transition metal chalcogenidogermanates [{Co(tepa)} 2 (μ‐Ge 2 S 6 )] ( 1 ) and [{M(tepa)} 2 (μ‐Ge 2 Se 6 )] (M = Mn ( 2 ), Fe ( 3 ); tepa = tetraethylenepentamine) were synthesized with GeO 2 , S(Se) and transition metal chloride as starting materials in tepa under solvothermal conditions. Complexes 1 – 3 crystallize in isostructural tetragonal space group I 4 1 / a . In 1 – 3 , the hexachalcogenidodigermanate anions are composed of two GeS 4 or GeSe 4 tetrahedra sharing a common edge, and act as bridging ligands by the trans terminal chalcogen atoms to link two [M(tepa)] 2+ cations, resulting in neutral complexes. All transition metal ions are in octahedral coordination environment involved in five nitrogen atoms and one chalcogen atom. Hydrogen bonds lead to three‐dimensional networks of [{Co(tepa)} 2 (μ‐Ge 2 S 6 )] and [{M(tepa)} 2 (μ‐Ge 2 Se 6 )] moieties in the crystal structures. TG‐DSC curves show that 1 – 3 get rid of tepa ligands in 180–400 °C temperature range when heated under nitrogen stream.