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})]

Journal Article · Sat Aug 15 00:00:00 EDT 2009 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.05.022· OSTI ID:21370523

Krivovichev, Sergey V ^[1]; Depmeier, Wulf ^[2]

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1. Department of Crystallography, St.Petersburg State University, 199034 St.Petersburg (Russian Federation)
2. Institut fuer Geowissenschaften, Universitaet Kiel, D-24118 Kiel (Germany)

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 of 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.

• OSTI ID: 21370523
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 8 Vol. 182; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ACTINIDE COMPOUNDS
ALKALI METAL COMPOUNDS
ANIONS
ARSENATES
ARSENIC COMPOUNDS
CHARGED PARTICLES
CHEMICAL COMPOSITION
CRYSTAL LATTICES
CRYSTAL STRUCTURE
IONS
MONOCLINIC LATTICES
ORTHORHOMBIC LATTICES
OXYGEN COMPOUNDS
PHOSPHATES
PHOSPHORUS COMPOUNDS
RUBIDIUM COMPOUNDS
RUBIDIUM IONS
SYNTHESIS
URANIUM COMPOUNDS
URANYL COMPOUNDS
URANYL PHOSPHATES