Ba8Hg3U3S18: A Complex Uranium(+4)/Uranium(+5) Sulfide
The compound Ba8Hg3U3S18 was obtained from the solid-state reaction at 1123 K of U, HgS, BaS, and S, with BaBr2/KBr or BaCl2 as a flux. This material crystallizes in a new structure type in space group P6̅ of the hexagonal system with three formula units in a cell of dimensions a = 27.08(1) Å, c = 4...
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Published in | Inorganic chemistry Vol. 51; no. 1; pp. 661 - 666 |
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Main Authors | , |
Format | Journal Article |
Language | English |
Published |
United States
American Chemical Society
02.01.2012
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Online Access | Get full text |
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Summary: | The compound Ba8Hg3U3S18 was obtained from the solid-state reaction at 1123 K of U, HgS, BaS, and S, with BaBr2/KBr or BaCl2 as a flux. This material crystallizes in a new structure type in space group P6̅ of the hexagonal system with three formula units in a cell of dimensions a = 27.08(1) Å, c = 4.208(2) Å, and V = 2673(2) Å3. The structure contains infinite chains of US6 octahedra and nearly linear [S–Hg–S]2– dithiomercurate anions, separated by Ba2+ cations. In the temperature range 100–300 K, the paramagnetic behavior of Ba8Hg3U3S18 can be fit to the Curie–Weiss law, resulting in μeff = 5.40(4) μB, or 3.12(2) μB/U. The compound displays an antiferromagnetic transition at T N = 59 K. Although the formal oxidation states of Ba, Hg, and S can be assigned as +2, +2, and –2, the oxidation state of U is less certain. On the basis of interatomic distance arguments and the magnetic susceptibility data, the compound is proposed to contain U in both +4 and +5 formal oxidation states. |
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Bibliography: | ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 |
ISSN: | 0020-1669 1520-510X |
DOI: | 10.1021/ic202161y |