Crystal structure of (Bi0.94Sb1.06)S3 and reconsideration of cation distribution over mixed sites in the bismuthinitestibnite solid-solution series

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The intermediate member of the (Bi,Sb)(2)S-3 solid-solution series was prepared by dry synthesis at low temperature (200 degrees C) with a long annealing period in sealed silica tube. The EDS analysis yielded an empirical formula (Bi0.96Sb1.04)S-3, which is very close to the formula (Bi0.94Sb1.06)S-3 obtained by crystal structure analysis. The crystal structure was refined to the R-factors: R-1 = 0.0288 for I > 2 sigma(I) and wR(2) = 0.0542 for all data. (Bi0.94Sb1.06)S-3 has orthorhombic symmetry with space group Pnma (No. 62). The asymmetric unit contains two independent mixed cation sites, both coordinated to seven S atoms in a form of mono-capped trigonal prism. They combine into infinite (M4S6)(n) rods parallel to the [010] direction with only weak interactions between rods where the lone electron pairs are directed. Our data and the revaluation of previous data resolve a controversy about the distribution of Sb and Bi over the two structural sites which exists in previously published works. It is shown that the structural constraints favour a slight preference of the larger cation for the marginal M1 site over the whole span of the solid-solution series. The unit cell parameters show a deviation form the Vegard's law connected with different rates of the parallel increase of lengths of the strong bonds and the decreasing influence of the lone electron pair with the replacement of Sb by Bi. The changes in the character of the two independent cation sites introduced by this replacement are similar to those produced during compression of Sb2S3.
Original languageEnglish
JournalNeues Jahrbuch für Mineralogie - Abhandlungen / Journal of Mineralogy and Geochemistry
Issue number2
Pages (from-to)177-187
Number of pages11
Publication statusPublished - 2012

ID: 49588941