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Solvothermal synthesis of three new dimeric thiogermanates (enH)4Ge2S6, [Mn(en)3]2Ge2S6 and [Ni(en)3]2Ge2S6 from germanium dioxide and sulfur powder
Authors:Ding-Xian Jia  Qin-Yu Zhu  Hai-Hong Lin
Institution:a Department of Chemistry and Chemical Engineering, Suzhou University, Number 1, Shizi Street, Suzhou City, Jiangsu Province 215006, P.R. China
b State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, P.R. China
Abstract:Three new thiogermanates (enH)4Ge2S6 (1) and M(en)3]2Ge2S6 (M=Mn (2), Ni (3); en=ethylenediamine) were synthesized using GeO2 and S8 as starting materials in molar ratio of 1:0.5 under solvothermal conditions. These compounds suggest that the dimeric Ge2S6]4− anion is likely to be the main germanium-containing species in en system and it also might be preferred as counter anions by the transition metal complex cations in crystallization. The cations of Mn(en)3]2+ and Ni(en)3]2+ are even better mineralizers than the protonated amine of enH]+. The crystal systems of Ge2S6]4− compounds are related to entities of cations and intermolecular reactions between cations and Ge2S6]4− anions. The compounds remove ethylenediamine and H2S molecules in multi steps when being heated under nitrogen stream.
Keywords:Solvothermal synthesis  Crystal structure  Thiogermanates  Thermoanalysis  Ethylenediamine
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