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Title: Rubidium uranyl phosphates and arsenates with polymeric tetrahedral anions: Syntheses and structures of Rb{sub 4}[(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)], Rb{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7})(P{sub 4}O{sub 12})] and Rb[(UO{sub 2}){sub 2}(As{sub 3}O{sub 10})]

The three new framework Rb uranyl phosphates and arsenates with anionic parts based on different type of polymeric anions have been prepared by high-temperature solid-state reactions: Rb{sub 4}[(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)] (1), Rb{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7})(P{sub 4}O{sub 12})] (2), Rb[(UO{sub 2}){sub 2}(As{sub 3}O{sub 10})] (3). The crystal structures of the synthesized compounds have been solved by direct methods: 1-monoclinic P2{sub 1}/c, a=9.672(1) A, b=12.951(1) A, c=32.231(3) A, beta=90.116(4){sup o}, V=4037.3(6) A{sup 3}, Z=4, R{sub 1}=0.0926 for 6351 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-monoclinic, P2{sub 1}/c, a=6.791(1) A, b=16.155(3) A, c=19.856(4) A, beta=97.48(5){sup o}, V=2159.8(7) A{sup 3}, Z=4, R{sub 1}=0.0286 for 3617 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-orthorhombic, Pbcn, a=10.558(1) A, b=11.037(1) A, c=11.464(1) A, V=1335.9(2) A{sup 3}, Z=4, R{sub 1}=0.0489 for 1384 unique reflections with |F{sub 0}|>=4sigma{sub F}. The structures of title are compounds based on 3D negatively charged frameworks with chemical compositions [(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)]{sup 4-} in 1, [(UO{sub 2}){sub 3}(P{sub 2}O{sub 7})(P{sub 4}O{sub 12})]{sup 2-} in 2 and [(UO{sub 2}){sub 2}(As{sub 3}O{sub 10})]{sup -} in 3. These negative charges are compensated by rubidium cations which are in the channels of 1 and closed cages in structures ofmore » 2 and 3. The channels in 1 are directed along the a direction and have minimum dimensions approx5 Ax6 A. This is the first example of porosity generation through solid state synthesis in uranyl compounds. For the first time in uranium chemistry polymeric anionic groups P{sub 4}O{sub 12} and As{sub 3}O{sub 10} were observed in structure of 2 and 3. - Graphical abstract: The polyhedral (a) and topological (b) representation of the Rb{sub 4}[(UO{sub 2}){sub 6}(P{sub 2}O{sub 7}){sub 4}(H{sub 2}O)] crystal structure.« less
Authors:
 [1] ;  [2] ;  [3] ;  [2] ;  [1]
  1. Institut fuer Geowissenschaften, Universitaet Kiel, D-24118 Kiel (Germany)
  2. (Russian Federation)
  3. Department of Crystallography, St.Petersburg State University, 199034 St.Petersburg (Russian Federation)
Publication Date:
OSTI Identifier:
21370523
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 182; Journal Issue: 8; Other Information: DOI: 10.1016/j.jssc.2009.05.022; PII: S0022-4596(09)00232-1; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ANIONS; ARSENATES; CHEMICAL COMPOSITION; MONOCLINIC LATTICES; ORTHORHOMBIC LATTICES; RUBIDIUM COMPOUNDS; RUBIDIUM IONS; SYNTHESIS; URANYL PHOSPHATES ACTINIDE COMPOUNDS; ALKALI METAL COMPOUNDS; ARSENIC COMPOUNDS; CHARGED PARTICLES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; IONS; OXYGEN COMPOUNDS; PHOSPHATES; PHOSPHORUS COMPOUNDS; URANIUM COMPOUNDS; URANYL COMPOUNDS