The two polymorphs of TlPbSbS3 and the structural relations of phases in the system TlSbS2-PbS

Abstract

The synthetic TlPbSbS3 represents a rare example of a sulphosalt with statistical distribution of Tl, Pb and Sb in the structure. Within the TlSbS2-PbS system, TlPbSbS3 is the end member of the solid solution series with TlSbS2, but no solubility with PbS is detected. The high temperatureβ-TlPbSbS3 is orthorhombic and inverts at about 620 K to the low-temperatureα phase. The low-temperature modification of TlPbSbS3 was structurally investigated by X-ray powder diffraction and by the Rietveld analysis of the data. The structure is monoclinic, with a = 4.1707(4) A, b = 4.2856(4) A, c = 12.157(1) A,β = 105.49(1)°, space group P21/c. Like in the high-temperature form, there is a cation disorder over the equivalent positions in the structure. The interatomic distances of (Tl, Ph, Sb) to S are 2.71, 2.72, 2.88, 3.15, 3.29, 3.51 (A). There is a close similarity between the TlPbSbS3 polymorphs and theα andβ forms of SnS, as regards the atomic coordinations and the general structure types and the same type of phase transformation is supposed for both cases. The small differences in the structure type and symmetry, between the low temperature forms of SnS and TlPbSbS3, result probably from stronger metal-metal interactions in the latter. A substitution-derivative relation to SnS type is established owing to the strong structural effect of the lone electron pairs of Tl and Sb. The substitution of Ag for Tl and Bi for Sb in ABCS3 type compounds diminishes this effect and PbS type structures are produced.