Solvothermal Syntheses and Characterization of New Transition Metal Chalcogenidogermanates [{Co(tepa)}2(μ-Ge2S6)] and [{M(tepa)}2(μ-Ge2Se6)] (M = Mn, Fe) (tepa = Tetraethylenepentamine)

New transition metal chalcogenidogermanates [{Co(tepa)}(2)-(mu-Ge2S6)] (1)and [{M(tepa)}(2)(mu-Ge2Se6)] (M = Mn (2), Fe (3); tepa = tetraethylenepentamine) were synthesized with GeO2, S(Sc) and transition metal chloride as starting, materials in tepa under solvothermal conditions. Complexes 1-3 crystallize in isostructural tetragonal space group 14(1)/a. In 1-3, the hexachalcogenidodigermanate anions are composed of two GeS4 or GeSC4 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)(mu-Ge2S6)] and [{M(tepa)}(2)(mu-Ge2Se6)] moieties in the crystal structures. TG-DSC curves show that 1-3 get rid of tepa ligands in 180-400 degrees C temperature range when heated under nitrogen stream.