Zur Kenntnis der Hydrate M(HSeO3)2 · 4H2O (M = Mg,Co, Ni,Zn). Röntgenstrukturanalytische,schwingungsspektroskopische und thermoanalytische Untersuchungen |
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| Authors: | B Engelen K Boldt K Unterderweide U Bumer |
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| Institution: | B. Engelen,K. Boldt,K. Unterderweide,U. Bäumer |
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| Abstract: | On the Hydrates M(HSeO3)2 · 4H2O (M = Mg, Co, Ni, Zn) – Crystal Structures, IR, Raman, and Thermoanalytical Investigations From aqueous solutions of M(HSeO3)2 single crystals of Mg(HSeO3)2 · 4H2O and of the hitherto unknown compounds Co(HSeO3)2 · 4H2O, Ni(HSeO3)2 · 4H2O and Zn(HSeO3)2 · 4H2O could be obtained. The crystal structures, X-ray powder, IR, Raman and thermoanalytical (DTA, TG, Raman heating) data are presented and discussed. The crystal data of the isotypic compounds are: monoclinic, space group C2/c, Z = 4, Mg: a = 1 464.6(2), b = 755.3(1), c = 1 099.9(1) pm, β = 126.59(1)°, V = 0.9769(1) nm3, Co: a = 1 462.5(2), b = 756.5(2), c = 1 102.2(2) pm, β = 126.53(1)°, V = 0.9798(2) nm3, Ni: a = 1 452.2(2), b = 751.0(1), c = 1 091.5(1) pm, β = 126.28(1)°, V = 0.9595(1) nm3, Zn: a = 1 468.3(2), b = 755.8(1), c = 1 103.1(1) pm, β = 126.79(1)°, V = 0.9804(2) nm3. The crystal structures consist of hexagonal packed M(HSeO3)2 · 2H2O]n chains of MO4(H2O)2] octahedra linked by Se atoms. They contain trigonal pyramidal SeO2OH?ions with “free” hydroxyl groups and also “free” molecules of water of crystallization. The hydroxyl groups build strong H-bonds (O? H …? O distances: 265–268 pm). The IR spectra show AB doublett bands in the OH stretching mode region of the hydroxyl groups. The water molecules of crystallization are linked to planar (H2O)4 tetramers by H-bonds with unusually short O? H …? O bond distances of 271–273 pm. DTA and TG measurements indicate that thermal decomposition results in the direct formation of the respective diselenite MSe2O5. Raman heating measurements show under quasi static conditions the intermediate formation of the anhydrous hydrogen selenites. |
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| Keywords: | Hydrogen selenites crystal structure IR Raman heating thermal analysis |
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