Two modifications of a new mercury sulfohalide of Hg
3S
2Br
2−x
Cl
x (
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 Hg
3S
2(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) Å
3, space group
C2/
m,
Z = 8,
R = 0.0513; II:
a = 18.248(2) Å,
V = 6076.4(12) Å
3, space group
Pm3¯
n,
Z = 32,
R = 0.038) has shown that they are polymorphous modifications of the compound of Hg
3S
2Br
1.5Cl
0.5 formula. The monoclinic modification I is isostractural to the synthetic compound α-Hg
3S
2Br
2. Modification II is isostructural to synthetic β-Hg
3S
2Cl
2. In both structures, each atom S has in its surrounding three atoms of Hg forming umbrella-type groups SHg
3 with spaces Hg—S 2.366–2.430 Å and angles HgSHg 95.66–97.60°. SHg
3-fragments are bound by Hg-apices with the formation of isolated cubic groups [Hg
12S
8]. 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
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 47, No. 2, pp. 318–323, March–April, 2006.