Tl2S: Re-Determination of Crystal Structure and Stereochemical Discussion
- Author(s)
- Gerald Giester, Christian Lengauer, Ekkehart Tillmanns, Josef Zemann
- Abstract
The crystal structure of synthetic carlinite, Tl2S, was redetermined by single crystal and powder X-ray diffraction methods. The cell parameters obtained from Rietveld refinement are a = 12.150(2) A°, c = 18.190(4) A°, V= 2325.5(7) A°3. A single crystal data refinement proved Tl2S crystallizing in the trigonal space group R3 with M = 440.8gmol-1, Z = 27, R = 0.076, and wR = 0.145. The atomic arrangement found is that of a strongly deformed anti-CdI2 type, but the deformation is clearly different from that given by previous workers. In the five crystallographically different STl6 octahedra the S-Tl distances vary between 2.82 and 3.09 A°, the Tl-Tl edges between 3.52 and 4.58 A°. The common features of these octahedra are (i) each one with a definitely smaller vs larger Tl3 face in transposition, both faces parallel or sub-parallel (00.1), and (ii) each three shorter and longer S-Tl distances to the atoms of the larger and smaller Tl3 faces, respectively. The Tl-Tl contacts between different Tl2S sheets are on the average definitely shorter than the ones within the sheet and they can be smaller than the Tl-Tl contacts in the small Tl3 faces of the STl6 octahedra. The atomic arrangement indicates that the single electron pairs of the monovalent Tl atoms are not arranged all parallel to the z-axis, as one would expect for Tl2S with an ideal anti-CdI2 structure. The surrounding of the S atoms resembles that of one-third of the Cl atoms in yellow InCl. The absorbance of Tl2S is very low at wave numbers approximately
- Organisation(s)
- Department of Mineralogy and Crystallography
- Journal
- Journal of Solid State Chemistry
- Volume
- 168
- Pages
- 322-330
- No. of pages
- 9
- ISSN
- 0022-4596
- DOI
- https://doi.org/10.1006/jssc.2002.9711
- Publication date
- 2002
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 1051 Geology, Mineralogy
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/33332aca-8aea-45f5-9e81-d2b046d0011e