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Synthesis and crystal structure of cesium actinide(VI) tricarbonate complexes Cs4AnO2(CO3)3·6H2O, An(VI) = U, Np, Pu

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Abstract

Tricarbonate complexes of hexavalent U, Np, and Pu with outer-sphere cesium cations, Cs4AnO2·(CO3)3·6H2O, were synthesized and studied by single crystal X-ray diffraction analysis. Crystals of Cs4AnO2·(CO3)3·6H2O consist of [AnO2(CO3)3]4– complex anions and hydrated Cs+ cations. The coordination polyhedron (CP) of An(VI) atoms is a distorted hexagonal bipyramid with three CO 2–3 anions arranged in the equatorial plane. Four independent Cs+ cations have the coordination surrounding in the form of 11-, 10-, and 9-vertex polyhedra formed by the O atoms of CO 2–3 anions, AnO 2+2 cations, and water molecules. Six crystallographically independent water molecules in the structure of Cs4AnO2(CO3)3·6H2O form a three-dimensional system of hydrogen bonds in which the O atoms of carbonate ions and water molecules act as proton acceptors. The “yl” oxygen atoms of AnO 2+2 cations are not involved in hydrogen bonding. The lengths of the An–Ocarb bonds in the equator of the U, Np, and Pu hexagonal bipyramids are noticeably influenced by incorporation of the O atoms of the CO 2–3 anions in the coordination polyhedra of Cs+ ions and by involvement of these atoms in hydrogen bonding.

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Authors and Affiliations

  1. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Leninskii pr. 31, korp. 4, Moscow, 119071, Russia

    I. A. Charushnikova, A. M. Fedoseev & V. P. Perminov

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  1. I. A. Charushnikova
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  2. A. M. Fedoseev
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  3. V. P. Perminov
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Correspondence to I. A. Charushnikova.

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Original Russian Text © I.A. Charushnikova, A.M. Fedoseev, V.P. Perminov, 2016, published in Radiokhimiya, 2016, Vol. 58, No. 6, pp. 496–501.

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Charushnikova, I.A., Fedoseev, A.M. & Perminov, V.P. Synthesis and crystal structure of cesium actinide(VI) tricarbonate complexes Cs4AnO2(CO3)3·6H2O, An(VI) = U, Np, Pu. Radiochemistry 58, 578–585 (2016). https://doi.org/10.1134/S1066362216060035

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  • DOI: https://doi.org/10.1134/S1066362216060035

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