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Comprehensive Uranium Thiophosphate Chemistry: Framework Compounds Based on Pseudotetrahedrally Coordinated Central Metal Atoms
Author(s) -
Neuhausen Christine,
Hatscher Stephan T.,
Panthöfer Martin,
Urland Werner,
Tremel Wolfgang
Publication year - 2013
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.201300300
Subject(s) - thiophosphate , chemistry , crystallography , orthorhombic crystal system , monoclinic crystal system , uranium , denticity , uranyl , tetragonal crystal system , crystal structure , metal , ternary operation , ion , materials science , organic chemistry , computer science , programming language , metallurgy
The new ternary compounds UP 2 S 6 , UP 2 S 7 , U(P 2 S 6 ) 2 , and U 3 (PS 4 ) 4 were prepared from uranium metal, phosphorus pentasulfide, and sulfur at 700 °C. The crystal structures were determined by single‐crystal X‐ray diffraction methods. UP 2 S 6 ( I ) crystallizes in the ZrP 2 S 6 structure type [tetragonal, P 4 2 / m , a = 6.8058(7) Å, c = 9.7597(14) Å, Z = 2], which consists of central uranium(IV) atoms coordinated by P 2 S 6 4– anions (staggered conformation). The anions are two‐dimensional connectors for four uranium cations arranged in one plane. The structure of UP 2 S 7 ( II ) [orthorhombic, Fddd , a = 8.9966(15) Å, b = 15.2869(2) Å, c = 30.3195(5) Å, Z = 16] is closely related to the monoclinic ZrP 2 S 7 structure type. It consists of U 4+ cations linked by P 2 S 7 4– ligands, the resulting 3D network contains large pores (diameter approx. 3.5 × 16.7 Å). In the previously reported compound U(P 2 S 6 ) 2 ( III ) [ I 4 1 / a , a = 12.8776(9) Å, c = 9.8367(10) Å, Z = 2], the metal atoms are coordinated by four bidentate P 2 S 6 2– ligands. This arrangement can be considered as a pseudotetrahedral coordination of the uranium atoms by the linear ligands. Three of the resulting diamondoid frameworks are inseparably interwoven in order to optimize space filling. U 3 (PS 4 ) 4 ( IV ) [ I 4 1 / acd , a = 10.7440(9) Å, c = 19.0969(2) Å, Z = 2] crystallizes in a defect variant of the PrPS 4 structure type, with 50 % of the U2 sites statistically occupied with uranium atoms. The resulting stoichiometry is U 3 (PS 4 ) 4 with tetravalent uranium atoms. The structure of U 3 (PS 4 ) 4 consists of uranium atoms connected by PS 4 3– groups, each PS 4 group linking four central uranium atoms. Vibrational spectra, which were recorded for I – III , show good agreement between the obtained results and the expected values for the anionic units, while magnetic measurements confirm the presence of tetravalent uranium.