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2004
Structure
D 2000
51- 005
Crystal Structure and Physical Properties of a New CuTi2S4 Modification in
Comparison to the Thiospinel. — The new rhombohedral modification of the title
compound is prepared directly from the elements at 425 °C. It crystallizes in space
group R3m with Z = 12 (single crystal XRD). Two topologically different interlayer
regions exist between the close-packed sulfide layers that alternate along the c axis: one
comprises both Cu (in tetrahedral voids) and Ti atoms (in octahedral voids), and the
second exclusively contains Ti atoms in octahedral voids. In contrast to the known
modification, the cubic spinel, Cu—Ti interactions of 2.88 Å occur that have bonding
character according to electronic structure calculations. The irreversible transformation
to the spinel takes place at temperatures above 450 C. Both CuTi2S4 modifications are
metallic Pauli paramagnets. — (SOHEILNIA, N.; KLEINKE, K. M.; DASHJAV, E.;
CUTHBERT, H. L.; GREEDAN, J. E.; KLEINKE*, H.; Inorg. Chem. 43 (2004) 20,
6473-6478; Dep. Chem., Univ. Waterloo, Waterloo, Ont. N2L 3G1, Can.; Eng.) —
Schramke
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