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Title: Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O]

Abstract

Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 for 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2,more » and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.« 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:
21372375
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 182; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2009.08.003; PII: S0022-4596(09)00380-6; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ARSENATES; CATIONS; LITHIUM IONS; MONOCLINIC LATTICES; MONOCRYSTALS; TETRAGONAL LATTICES; URANYL PHOSPHATES; ACTINIDE COMPOUNDS; ARSENIC COMPOUNDS; CHARGED PARTICLES; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; IONS; OXYGEN COMPOUNDS; PHOSPHATES; PHOSPHORUS COMPOUNDS; URANIUM COMPOUNDS; URANYL COMPOUNDS

Citation Formats

Alekseev, Evgeny V., E-mail: e_v_alekseev@mail.r, Nizhny Novgorod State University, 603950 Nizhny Novgorod, Krivovichev, Sergey V., Institute of Silicate Chemistry, Russian Academy of Sciences, 199034 St. Petersburg, and Depmeier, Wulf. Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O]. United States: N. p., 2009. Web. doi:10.1016/j.jssc.2009.08.003.
Alekseev, Evgeny V., E-mail: e_v_alekseev@mail.r, Nizhny Novgorod State University, 603950 Nizhny Novgorod, Krivovichev, Sergey V., Institute of Silicate Chemistry, Russian Academy of Sciences, 199034 St. Petersburg, & Depmeier, Wulf. Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O]. United States. doi:10.1016/j.jssc.2009.08.003.
Alekseev, Evgeny V., E-mail: e_v_alekseev@mail.r, Nizhny Novgorod State University, 603950 Nizhny Novgorod, Krivovichev, Sergey V., Institute of Silicate Chemistry, Russian Academy of Sciences, 199034 St. Petersburg, and Depmeier, Wulf. Sun . "Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O]". United States. doi:10.1016/j.jssc.2009.08.003.
@article{osti_21372375,
title = {Crystal chemistry of anhydrous Li uranyl phosphates and arsenates. II. Tubular fragments and cation-cation interactions in the 3D framework structures of Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})], Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})], Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O]},
author = {Alekseev, Evgeny V., E-mail: e_v_alekseev@mail.r and Nizhny Novgorod State University, 603950 Nizhny Novgorod and Krivovichev, Sergey V. and Institute of Silicate Chemistry, Russian Academy of Sciences, 199034 St. Petersburg and Depmeier, Wulf},
abstractNote = {Single crystals of the new compounds Li{sub 6}[(UO{sub 2}){sub 12}(PO{sub 4}){sub 8}(P{sub 4}O{sub 13})] (1), Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] (2), Li[(UO{sub 2}){sub 4}(AsO{sub 4}){sub 3}] (3) and Li{sub 3}[(UO{sub 2}){sub 7}(AsO{sub 4}){sub 5}O)] (4) have been prepared using high-temperature solid state reactions. The crystal structures have been solved by direct methods: 1-monoclinic, C2/m, a=26.963(3) A, b=7.063(1) A, c=19.639(1) A, beta=126.890(4){sup o}, V=2991.2(6) A{sup 3}, Z=2, R{sub 1}=0.0357 for 3248 unique reflections with |F{sub 0}|>=4sigma{sub F}; 2-triclinic, P1-bar, a=7.1410(8) A, b=13.959(1) A, c=31.925(1) A, alpha=82.850(2){sup o}, beta=88.691(2){sup o}, gamma=79.774(3){sup o}, V=3107.4(4) A{sup 3}, Z=2, R{sub 1}=0.0722 for 9161 unique reflections with |F{sub 0}|>=4sigma{sub F}; 3-tetragonal, I4{sub 1}/amd, a=7.160(3) A, c=33.775(9) A, V=1732(1) A{sup 3}, Z=4, R{sub 1}=0.0356 for 318 unique reflections with |F{sub 0}|>=4sigma{sub F}; 4-tetragonal, P4-bar, a=7.2160(5) A, c=14.6540(7) A, V=763.04(8) A{sup 3}, Z=1, R{sub 1}=0.0423 for 1600 unique reflections with |F{sub 0}|>=4sigma{sub F}. Structures of all the phases under consideration are based on complex 3D frameworks consisting of different types of uranium polyhedra (UO{sub 6} and UO{sub 7}) and different types of tetrahedral TO{sub 4} anions (T=P or As): PO{sub 4} and P{sub 4}O{sub 13} in 1, AsO{sub 4} and As{sub 2}O{sub 7} in 2, and single AsO{sub 4} tetrahedra in 3 and 4. In the structures of 1 and 2, UO{sub 7} pentagonal bipyramids share edges to form (UO{sub 5}){sub i}nfinity chains extended along the b axis in 1 and along the a axis in 2. The chains are linked via single TO{sub 4} tetrahedra into tubular units with external diameters of 11 A in 1 and 11.5 A in 2, and internal diameters of 4.1 A in 1 and 4.5 A in 2. The channels accommodate Li{sup +} cations. The tubular units are linked into 3D frameworks by intertubular complexes. Structures of 3 and 4 are based on 3D frameworks composed on layers united by (UO{sub 5}){sub i}nfinity infinite chains. Cation-cation interactions are observed in 2, 3, and 4. In 2, the structure contains a trimeric unit with composition [O=U(1)=O]-U(13)-[O=U(2)=O]. In the structures of 3 and 4, T-shaped dimers are observed. In all the structures, Li{sup +} cations are located in different types of cages and channels and compensate negative charges of anionic 3D frameworks. - Graphical abstract: The crystal structures of Li{sub 5}[(UO{sub 2}){sub 13}(AsO{sub 4}){sub 9}(As{sub 2}O{sub 7})] separated into tubular units and intertubular complexes.},
doi = {10.1016/j.jssc.2009.08.003},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 11,
volume = 182,
place = {United States},
year = {2009},
month = {11}
}