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Title: [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}], crystal structure and comparison with uranium minerals with U{sub 3}O{sub 8}-type sheets

The new U(VI) compound, [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}], was synthesized by mild hydrothermal reaction of uranyl and nickel nitrates. The crystal-structure was solved in the P-1 space group, a=8.627(2), b=10.566(2), c=12.091(4) A and alpha=110.59(1), beta=102.96(2), gamma=105.50(1){sup o}, R=0.0539 and wR=0.0464 from 3441 unique observed reflections and 151 parameters. The structure of the title compound is built from sheets of uranium polyhedra closely related to that in beta-U{sub 3}O{sub 8}. Within the sheets [(UO{sub 2})(OH)O{sub 4}] pentagonal bipyramids share equatorial edges to form chains, which are cross-linked by [(UO{sub 2})O{sub 4}] and [UO{sub 4}(H{sub 2}O)(OH)] square bipyramids and through hydroxyl groups shared between [(UO{sub 2})(OH)O{sub 4}] pentagonal bipyramids. The sheets are pillared by sharing the apical oxygen atoms of the [(UO{sub 2})(OH)O{sub 4}] pentagonal bipyramids with the oxygen atoms of [NiO{sub 2}(H{sub 2}O){sub 4}] octahedral units. That builds a three-dimensional framework with water molecules pointing towards the channels. On heating [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}] decomposes into NiU{sub 3}O{sub 10}. - Graphical abstract: The framework of [Ni(H{sub 2}O){sub 4}]{sub 3}[U(OH,H{sub 2}O)(UO{sub 2}){sub 8}O{sub 12}(OH){sub 3}] built from uranium polyhedra sheets pillared by Ni-centered octahedra.
Authors:
 [1] ; ; ;  [1]
  1. Unite de Catalyse et de Chimie du Solide, Equipe Chimie du Solide, UCCS UMR CNRS 8181, USTL, ENSC-B.P. 90108, 59652 Villeneuve d'Ascq Cedex (France)
Publication Date:
OSTI Identifier:
21370355
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 182; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2009.01.019; PII: S0022-4596(09)00024-3; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CRYSTAL STRUCTURE; HEATING; HYDROTHERMAL SYNTHESIS; NICKEL NITRATES; SHEETS; SPACE GROUPS; URANIUM DIOXIDE; URANIUM HYDROXIDES; URANIUM MINERALS; URANIUM OXIDES U3O8 ACTINIDE COMPOUNDS; CHALCOGENIDES; HYDROGEN COMPOUNDS; HYDROXIDES; MATERIALS; MINERALS; NICKEL COMPOUNDS; NITRATES; NITROGEN COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; RADIOACTIVE MATERIALS; RADIOACTIVE MINERALS; SYMMETRY GROUPS; SYNTHESIS; TRANSITION ELEMENT COMPOUNDS; URANIUM COMPOUNDS; URANIUM OXIDES