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Radiochemistry

, Volume 60, Issue 5, pp 514–520 | Cite as

Complexes of An(VI) with Cyclobutanecarboxylic Acid Anions and Outer-Sphere Alkali Metal Cations

  • M. S. Grigor’ev
  • I. A. CharushnikovaEmail author
  • A. M. Fedoseev
Article
  • 10 Downloads

Abstract

New complexes of hexavalent actinides with cyclobutanecarboxylic acid (Hcbc) anions, Na4[NpO2· (cbc)3]4·H2O (I), K[NpO2(cbc)3] (II), Cs[NpO2(cbc)3] (III), and Cs[PuO2(cbc)3] (IV), cbc = C4H7(COO), were synthesized and studied by single crystal X-ray diffraction. The structures of I–IV are based on the anionic complexes [AnO2(cbc)3] surrounded by alkali metal cations. The AnO 2 2+ cation in the anionic complex is bonded with three chelating C4H7COO anions, and the coordination polyhedron (CP) of An is a hexagonal bipyramid with the O atoms of the AnO 2 2+ cations in apical positions. The coordination number (CN) of the alkali metal cations in the structures of II–IV is the same and equal to 6; the coordination surrounding of the K+ and Cs+ cations is constituted by the O atoms of six C4H7COO anions. The crystal structures of IIIV are examples of cubic 3-connected networks (10,3) built of alkali metal and actinide cations. In the structure of I, there are four kinds of crystallographically different NpO 2 2+ and Na+ cations. The coordination surrounding of the NpO 2 2+ cations differs only in the conformational characteristics of the C4H7COO ligands. Four independent Na+ cations differ from each other in the structure of the coordination surrounding. The CPs of the Na(1) and Na(4) atoms can be described as distorted octahedra (CN 6); that of Na(3), as a trigonal prism (CN 6); and that of Na(2), as a tetragonal pyramid (CN 5) with one of the basal vertices occupied by the Ow(1) atom of a water molecule. In the structure of I, the configuration of the network formed by the Na and Np cations differs from the cubic 3-connected network found in the structures of IIIV.

Keywords

neptunium(VI) plutonium(VI) cyclobutanecarboxylic acid synthesis crystal structure 

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Copyright information

© Pleiades Publishing, Inc. 2018

Authors and Affiliations

  • M. S. Grigor’ev
    • 1
  • I. A. Charushnikova
    • 1
    Email author
  • A. M. Fedoseev
    • 1
  1. 1.Frumkin Institute of Physical Chemistry and ElectrochemistryRussian Academy of SciencesMoscowRussia

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