Volume 47, Number 2, 312-317, DOI: 10.1007/s10947-006-0301-0

Crystallochemistry of mercury chalcogenides. IV. Crystalline structure of two polymorphous modifications of the mercury sulfochalcogenide Hg3S2Br1.5Cl0.5

N. V. Pervukhina, S. A. Magarill, D. Yu. Naumov, S. V. Borisov, V. I. Vasil’yev and B. G. Nenashev

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Abstract

Two modifications of a new mercury sulfohalide of Hg3S2Br2−x Clx (x = 0.5) composition have been grown from the gas phase and explored by X-ray structural analysis. The compounds were obtained at an attempt to synthesize an analogue of the rare mineral arzakite Hg3S2(Br, Cl)2 (Br > Cl). The refinement of the crystalline structures of monoclinic (I) and cubic (II) phases (I: a = 17.824(4) Å, b = 9.238(2) Å, c = 10.269(2) Å, β = 115.69(1)°, V = 1523.8(5) Å3, space group C2/m, Z = 8, R = 0.0513; II: a = 18.248(2) Å, V = 6076.4(12) Å3, space group Pmn, Z = 32, R = 0.038) has shown that they are polymorphous modifications of the compound of Hg3S2Br1.5Cl0.5 formula. The monoclinic modification I is isostractural to the synthetic compound α-Hg3S2Br2. Modification II is isostructural to synthetic β-Hg3S2Cl2. In both structures, each atom S has in its surrounding three atoms of Hg forming umbrella-type groups SHg3 with spaces Hg—S 2.366–2.430 Å and angles HgSHg 95.66–97.60°. SHg3-fragments are bound by Hg-apices with the formation of isolated cubic groups [Hg12S8]. Like that in other structures of mercury chalcohalides, the main role in structure-forming of the investigated compounds is played by atoms of halogens creating a cubic sublattice in which radicals Hg—S are arranged.

Keywords  mercury - chalcohalides of mercury - mercury minerals - crystalline structure - X-ray structural analysis - isomorphism - polymorphism

Original Russian Text Copyright © 2006 by N. V. Pervukhina, S. A. Magarill, D. Yu. Naumov, S. V. Borisov, V. I. Vasil’yev, and B. G. Nenashev
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Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 318–323, March–April, 2006.

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