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Stanislav V. Borisov, Svetlana A. Magarill, Natalie V. Pervukhina

To crystal chemistry of compounds of MHgYX (M = Cu, Ag, Y = S, Se, X = Cl, Br, I)

In the crystal structures MHgYX (M = Cu, Ag, Y = S, Se, X = Cl, Br, I) and also in CuHg₂S₂I and Ag₂HgSI₂ the packing of anions X and Y varies from the hexagonal closest packing (CuHgSI, CuHg₂S₂I, and α-AgHgSI) to a cubic space-centered packing (Ag₂HgSI₂, CuHgSBr (295 K), β-AgHgSI, and CuHgSBr (358 K). The packing regularity for large (I^–) and smaller (S^2–) anions is ensured because Hg²⁺ has linear coordination S—Hg—S (S—S ∼ 4.5 Å), which is comparable with I—I contacts in a joint close packing. S^2–(Se^2–) are surrounded in a tetrahedral manner and form stable groups (Hg,M)₄Y where the most strong chemical bonds Hg—Y, M—Y, Hg—Hg (∼3.5 Å), Hg—M are concentrated. The chains, layers, and frameworks of (Hg,M)₄Y tetrahedra form a “skeleton” and, thus, determine the structure form and the sizes of elementary cells.

Zeitschrift für Kristallographie, Oldenbourg Wissenschaftsverlag

Print ISSN: 0044-2968
Volume: 220, 11/2005
Pages: 946 - 953

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