Abstract
Three different uranium trichloride hydrates of the formulas UCl 3 · 2H 2O · 2CH 3CN, UCl 3 · 6H 2O and UCl 3 · 7H 2O have been isolated from methylcyanide solutions of UCl 4, with a 1–5% water content, by reduction with liquid zinc amalgam. The crystal and molecular structures of the hydrates have been determined by X-ray single crystal analysis. UCl 3 · 2H 2O · 2CH 3CN crystallizes in the triclinic system (space group P 1 ¯ ) forming infinite zigzag chains in the [0 1 0] direction. The coordination polyhedron of the uranium atom is a bicapped trigonal prism, formed by two oxygen atoms of the water molecules, four bridging chlorine atoms, one terminal chlorine atom and one nitrogen atom of the methylcyanide molecule. UCl 3 · 6H 2O crystallizes in the monoclinic system (space group P2/ n), with a monomeric structure. The uranium ion is eight-coordinated by two chlorine atoms and six oxygen atoms of the water molecules, which form a distorted square antiprism. UCl 3 · 7H 2O crystallizes in the triclinic system in the space group P 1 ¯ . The characteristic feature of this structure are [(H 2O) 7UCl 2U(H 2O) 7] 4+ dimers. The coordination polyhedra, in the form of a tricapped trigonal prism, are linked through the complex network of the hydrogen bonds. UCl 3 · 6H 2O and UCl 3 · 7H 2O are isostructural with their lanthanide analogues.
Published Version
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