Using M?ssbauer spectroscopy to choose the sites that can be occupied by divalent tin
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- 作者：Georges Dénès (1)
Hocine Merazig (2)
Abdualhafed Muntasar (1) - 关键词：Wyckoff sites ; Site symmetry ; Lone pair stereoactivity ; Divalent tin ; M?ssbauer spectroscopy
- 刊名：Hyperfine Interactions
- 出版年：2014
- 出版时间：April 2014
- 年：2014
- 卷：226
- 期：1-3
- 页码：79-87
- 全文大小：
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Hocine Merazig (2)
Abdualhafed Muntasar (1)
1. Laboratory of Solid State Chemistry and M?ssbauer Spectroscopy, Department of Chemistry and Biochemistry, Concordia University, Montréal, Québec, Canada
2. Unité de Recherche de Chimie de l’Environnement et Moléculaire Structurale CHEMS, Département de Chimie, Faculté des Sciences, Université de Constantine 1, Constantine, Algeria - ISSN：1572-9540
文摘
M?ssbauer spectroscopy can be a useful structural tool to assist crystallographic methods for site assignment when the compound under investigation contains divalent tin. The goal of this work was to show that the structure of tin(II) fluoride, also know as stannous fluoride, SnF2, could have been solved 14 years earlier if M?ssbauer spectroscopic results, already known, had been used. A first attempt to solve the crystal structure, carried out by Bergerhoff in 1962 seemed to find the tin positions, however, it failed to find the positions of fluorine. Further extensive studies by Dénès et al. in the mid 1970s yielded the same results as those of Bergerhoff, despite the use of a Nonius CAD-4 automatic diffractometer, in contrast with Bergerhoff’s film work. The tin positions yielded a residual of 0.23, and Fourier difference maps showed significant electron density that could be fluorine atoms, however, their number did not match the number of fluorine atoms expected and several F-F distances were way too short. In addition, refinement using these possible fluorine positions led to no improvement of the residual factor. Finally, the crystal structure was published by McDonald et al. in 1976. It was found that the tin sublattice determined by Bergerhoff was basically correct, except that half of the tin atoms found by Bergerhoff to be on the (4b) and (4e) special Wyckoff sites were actually on the (8f) general site. A translation of the origin of the unit-cell by the [1/8, 0, 3/16] vector allows to change the tin Wyckoff sites from (4b), (4e) and (8f) to two (8f) sites, while keeping the basic spatial distribution of tin. A method has now been designed, using 119Sn M?ssbauer spectroscopy, to test the suitability of some Wyckoff sites for divalent tin, using the M?ssbauer spectrum. The tin(II) doublet (δ = 3.430(3) mm/s, Δ = 1.532(3) mm/s) shows that the lone pair is on a hybrid orbital, therefore, it is stereoactive, and it results that tin cannot be on either the (4b) or (4e) tin site since both an inversion center and a 2-fold axis would generate a second lone pair unless the 2-fold axis were along the tin-lone pair axis.