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Abstract

Crystal structures of a large number of complex sulphides can be described as composed of rods, blocks or layers of simple, archetypal structures that are joined (recombined) in various ways by the action of one or more structure-building operators, such as the various kinds of unit-cell twinning. The resulting structures were denoted as the recombination structures by the Subcommittee on the Nomenclature of Inorganic Structure Types (Lima-de-Faria et al., 1990). It is this kind of complex sulphides we deal with in the present review; those with complex chemistry but simple structural principles (e.g., the substitution-, interstitial- or omission derivatives of archetypal structures) are not included.

The principal sulphide family with recombination structures are the so-called “sulphosalts”. They are defined as complex sulphides (rarely also selenides and tellurides) AxBySz with A = Pb, Cu, Ag, Hg, Tl, Fe, Mn, Sn2+, Sn4+ and other metals; these may include alkali metals, alkaline earths, lanthanides and various organic cations in some synthetic sulphosalts; B = formally trivalent cations As, Sb and Bi in non-planar, (fundamentally) threefold coordination BS3; and S = S2−, Se2− and Te2−. Sn2+ and Te4+ have the same coordination properties as B3+ and it is difficult to draw a borderline between their sulphides and the sulphosalts sensu stricto.

Structurally very close to sulphosalts are (a) the complex sulphides of (primarily) octahedral In with Pb, Sn, Bi and other metals, (b) the layer misfit sulphides, based on a combination of layers that contain large cations (La to Sn, Y, Sn2+, Pb and Bi3+)

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