Abstract
New hybrid organic-inorganic complex zirconium and hafnium fluorides with the 4-amino-1,2,4-triazolium cation (C2H5N4)2MF6 (M = Zr, Hf, Zr x Hf1–x ), which crystallize in two polymorphs (monoclinic (P21/n, Z = 4) and triclinic (P \(\overline 1 \), Z = 2)) are synthesized and structurally studied for the first time. The structures of both polymorphs are composed of hydrogen bonded (N–H•••F and C–H•••F) 4-amino-1,2,4-triazolium cations protonated via the nitrogen atom in site 1 and complex [M2F12]4− anions that are centrosymmetric dimers formed by edge-sharing pentagonal bipyramids MF7 (M = Zr, Hf, Zr x Hf1–x ). It is found that in the structures studied 4-amino-1,2,4-triazolium cation occur simultaneously as cis- and trans-conformers. The packing character of structural units in the unit cells of the studied crystals is discussed along with the structure of the neutral and protonated forms of 4-amino-1,2,4-triazole.
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Original Russian Text © 2015 A. V. Gerasimenko, R. L. Davidovich, M. A. Pushilin, V. B. Logvinova.
Translated from Zhurnal Strukturnoi Khimii, Vol. 56, No. 8, pp. 1648-1656, December, 2015.
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Gerasimenko, A.V., Davidovich, R.L., Pushilin, M.A. et al. Structure of polymorphs of complex zirconium and hafnium fluorides with the 4-amino-1,2,4-triazolium cation: (C2H5N4)2MF6 (M = Zr, Hf, Zr x Hf1–x ). J Struct Chem 56, 1586–1594 (2015). https://doi.org/10.1134/S002247661508020X
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DOI: https://doi.org/10.1134/S002247661508020X