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Effect of the partial substitution of sulfur by selenium on the atomic arrangement in sulfate- and selenate-based compounds

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Abstract

Two new co-based hybrid materials, (C4H12N2)[Co(H2O)6](S0.689Se0.311O4)2 (1) and (C4H12N2)[Co(H2O)6](S0.80Se0.20O4)2 (2), have been synthesized by slow evaporation method at room temperature and crystallographically characterized. They crystallizes isotypically in the monoclinic system, space group C2/c, with the following unit-cell parameters: a = 14.2559(19), b = 9.5066(13), c = 13.6759(19) Å, β = 114.930(4)°, V = 1680.7(4) Å3, and Z = 4 for (1) and a = 14.2235(19), b = 9.4901(14), c = 13.666(2) Å, β = 114.863(4)°, V = 1673.7(4) Å3, and Z = 4 for (2). Their crystal structure consist of metallic cations octahedrally coordinated by six water molecules [Co(H2O)6]2+, piperazinediium cations (C4H12N2)2+, and sulfate/selenate anions (S x Se1-x O4)2− linked together via two types of hydrogen bonds, Ow–H···O and N–H···O. The IR spectroscopic study confirms not only the substitution of the sulfur by the selenium but also the piperazine protonation. Through this work, it is demonstrated that the substitution of sulfur by selenium atom can lead to strong modification in the space group and atomic arrangement. Indeed the mixed selenate/sulfate compounds adopt a crystal structure different from those of the pure sulfate or selenate phases. The thermogravimetric measurement indicates that the dehydration occurs in two steps by the departure of six water molecules giving rise to an anhydrous phase. The final product of the decomposition is cobalt oxide, CoO, in both cases.

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Authors and Affiliations

  1. Laboratoire Physico-Chimie de l’Etat Solide, Faculté des Sciences de Sfax, Université de Sfax, B.P. 1171, 3000, Sfax, Tunisia

    Ines Kadri, Marwa Abid Derbel, Houcine Naïli & Walid Rekik

  2. Centre de Diffractométrie X, Institut des Sciences Chimiques de Rennes (ISCR), UMR 6226 CNRS-Université de Rennes 1, Campus de Beaulieu, 263 avenue du General Leclerc, Bat 10A, 35042, Rennes Cedex, France

    Thierry Roisnel

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  1. Ines Kadri
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Correspondence to Walid Rekik.

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Kadri, I., Derbel, M.A., Naïli, H. et al. Effect of the partial substitution of sulfur by selenium on the atomic arrangement in sulfate- and selenate-based compounds. Chem. Pap. 71, 2063–2073 (2017). https://doi.org/10.1007/s11696-017-0199-3

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