拓展过氧酰基化合物的晶体化学：Na5[(UO2)3(O2)4(OH)3](H2O)13中铀酰多面体的开放片层

Expanding the crystal chemistry of actinyl peroxides: open sheets of uranyl polyhedra in Na5[(UO2)3(O2)4(OH)3](H2O)13.

作者信息

Kubatko Karrie-Ann, Burns Peter C

机构信息

Department of Civil Engineering and Geological Sciences, University of Notre Dame, 156 Fitzpatick Hall, Notre Dame, IN 46556, USA.

出版信息

Inorg Chem. 2006 Aug 7;45(16):6096-8. doi: 10.1021/ic0518677.

DOI:10.1021/ic0518677

PMID:16878908

Abstract

A uranyl peroxide, Na5(UO2)3(O2)4(OH)313, with an open sheet of uranyl polyhedra has been synthesized under ambient conditions and structurally characterized. The structure (orthorombic, Cmca, a = 23.632(1) A, b = 15.886(1) A, c = 13.952(1) A, V = 5237.7 A(3), and Z = 8) consists of sheets composed of two symmetrically unique uranyl (UO2)2+ ions that are coordinated equatorially by two peroxide groups and two OH(-) groups, forming distorted uranyl hexagonal bipyramids of composition (UO2)(O2)2(OH)2(4-). The uranyl bipyramids are connected into sheets with openings with dimensions 13.7 A along [010] and 15.9 A along [100]. The shortest dimension of the cavity is 8.08 A. Sheets of two-dimensionally polymerized uranyl polyhedra are the most common structural type of inorganic uranyl phases; however, such an open topology has never been observed.

摘要

一种过氧化铀酰，Na5(UO2)3(O2)4(OH)313，其具有由铀酰多面体构成的开放片层结构，已在环境条件下合成并进行了结构表征。该结构（正交晶系，Cmca，a = 23.632(1) Å，b = 15.886(1) Å，c = 13.952(1) Å，V = 5237.7 Å(3)，Z = 8）由片层组成，该片层由两个对称独特的铀酰（UO2）2+离子构成，它们由两个过氧基团和两个OH(-)基团在赤道面配位，形成组成式为（UO2）(O2)2(OH)2(4-)的扭曲铀酰六方双锥。铀酰双锥连接成具有开口的片层，开口在[010]方向尺寸为13.7 Å，在[100]方向尺寸为15.9 Å。空腔的最短尺寸为8.08 Å。二维聚合的铀酰多面体片层是无机铀酰相最常见结构类型；然而，这种开放拓扑结构从未被观察到。