Department of Civil Engineering and Geological Sciences, University of Notre Dame, Notre Dame, Indiana 46556, United States.
Inorg Chem. 2011 Mar 21;50(6):2272-7. doi: 10.1021/ic1019444. Epub 2011 Feb 3.
The isomorphous compounds NH(4)[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (1), K[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (2), Li(3)O[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (3), and Ba[(UO(6))(2)(UO(2))(9)(GeO(4))(2)] (4) were synthesized by hydrothermal reaction at 220 °C. The structures were determined using single crystal X-ray diffraction and refined to R(1) = 0.0349 (1), 0.0232 (2), 0.0236 (3), 0.0267 (4). Each are trigonal, P(3)1c. 1: a = 10.2525(5), c = 17.3972(13), V = 1583.69(16) Å(3), Z = 2; 2: a = 10.226(4), c = 17.150(9), V = 1553.1(12) Å(3), Z = 2; 3: a = 10.2668(5), c = 17.0558(11), V = 1556.94(15) Å(3), Z = 2; 4: a = 10.2012(5), c = 17.1570(12), V = 1546.23(15) Å(3), Z = 2. There are three symmetrically independent U sites in each structure, two of which correspond to typical (UO(2))(2+) uranyl ions and the other of which is octahedrally coordinated by six O atoms. One of the uranyl ions donates a cation-cation interaction, and accepts a different cation-cation 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.
采用水热法在 220°C 下合成了同晶化合物 NH(4)[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (1)、K[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (2)、Li(3)O[(UO(6))(2)(UO(2))(9)(GeO(4))(GeO(3)(OH))] (3)和 Ba[(UO(6))(2)(UO(2))(9)(GeO(4))(2)] (4)。通过单晶 X 射线衍射确定了结构，并将其精修至 R(1) = 0.0349 (1)、0.0232 (2)、0.0236 (3)、0.0267 (4)。它们均为三方晶系，P(3)1c。1：a = 10.2525(5)，c = 17.3972(13)，V = 1583.69(16) Å(3)，Z = 2；2：a = 10.226(4)，c = 17.150(9)，V = 1553.1(12) Å(3)，Z = 2；3：a = 10.2668(5)，c = 17.0558(11)，V = 1556.94(15) Å(3)，Z = 2；4：a = 10.2012(5)，c = 17.1570(12)，V = 1546.23(15) Å(3)，Z = 2。在每个结构中都有三个对称独立的 U 位，其中两个对应于典型的(UO(2))(2+)铀酰离子，另一个则由六个 O 原子配位形成八面体。一个铀酰离子提供一个阳离子-阳离子相互作用，并接受另一个阳离子-阳离子相互作用。U 多面体之间的连接导致了相对密集的三维骨架。Ge 和低价位位于 U 多面体骨架的空腔内。提供了化学、热和光谱特性。
