U(VI) Uranyl Cation鈭扖ation Interactions in Framework Germanates
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- 作者：Jessica M. Morrison ; Laura J. Moore-Shay ; Peter C. Burns
- 刊名：Inorganic Chemistry
- 出版年：2011
- 出版时间：March 21, 2011
- 年：2011
- 卷：50
- 期：6
- 页码：2272-2277
- 全文大小：781K
- 年卷期：v.50,no.6(March 21, 2011)
- ISSN：1520-510X
文摘
The isomorphous compounds NH4[(UO6)2(UO2)9(GeO4)(GeO3(OH))] (1), K[(UO6)2(UO2)9(GeO4)(GeO3(OH))] (2), Li3O[(UO6)2(UO2)9(GeO4)(GeO3(OH))] (3), and Ba[(UO6)2(UO2)9(GeO4)2] (4) were synthesized by hydrothermal reaction at 220 掳C. The structures were determined using single crystal X-ray diffraction and refined to R1 = 0.0349 (1), 0.0232 (2), 0.0236 (3), 0.0267 (4). Each are trigonal, P3̅1c. 1: a = 10.2525(5), c = 17.3972(13), V = 1583.69(16) 脜3, Z = 2; 2: a = 10.226(4), c = 17.150(9), V = 1553.1(12) 脜3, Z = 2; 3: a = 10.2668(5), c = 17.0558(11), V = 1556.94(15) 脜3, Z = 2; 4: a = 10.2012(5), c = 17.1570(12), V = 1546.23(15) 脜3, Z = 2. There are three symmetrically independent U sites in each structure, two of which correspond to typical (UO2)2+ uranyl ions and the other of which is octahedrally coordinated by six O atoms. One of the uranyl ions donates a cation鈭抍ation interaction, and accepts a different cation鈭抍ation interaction. The linkages between the U-centered polyhedra result in a relatively dense three-dimensional framework. Ge and low-valence sites are located within cavities in the framework of U-polyhedra. Chemical, thermal, and spectroscopic characterizations are provided.