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Cation–cation interaction in mixed-element Th(IV)/Np(V) chlorides, [Th(NpO2)6(H2O)8(OH)Cl9]·H2O and [Th(NpO2)6(H2O)9Cl9]Cl

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Abstract

The compounds [Th(NpO2)6(H2O)8(OH)Cl9]·H2O (I) and [Th(NpO2)6(H2O)9Cl9]Cl (II), in which mixed-element Th(IV)/Np(V) cation–cation interaction is observed, were isolated in the form of single crystals and studied by X-ray diffraction. The NpO2 +···NpO2 + cation–cation bonds link the dioxocations into six-unit rings, and the NpO2 +···Th4+ bonds link these rings into a three-dimensional network. The compounds also contain a hydroxide ion incorporated in the Th4+ coordination surrounding or a chloride ion located in the interlayer space, depending on the synthesis conditions. The Np(V) pentagonal bipyramids in I and II are characterized by equal, within the uncertainty, bond lengths. The equatorial planes of the bipyramids are formed by three Cl– anions, oxygen atom of the adjacent NpO2 + cation, and oxygen atom of the water molecule. The Th4+ cations in I and II have the coordination surrounding in the form of tricapped trigonal prisms (CN 9) whose quadrangular lateral faces are formed by the oxygen atoms of the NpO2 + cations and are capped by three water molecules. The Th4+ cations in I and II are arranged in the interlayer space, binding three cyclic moieties from each of the two adjacent layers.

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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 & N. N. Krot

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  1. I. A. Charushnikova
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  2. A. M. Fedoseev
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  3. N. N. Krot
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Correspondence to I. A. Charushnikova.

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Original Russian Text © I.A. Charushnikova, A.M. Fedoseev, N.N. Krot, 2016, published in Radiokhimiya, 2016, Vol. 58, No. 5, pp. 385–389.

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Charushnikova, I.A., Fedoseev, A.M. & Krot, N.N. Cation–cation interaction in mixed-element Th(IV)/Np(V) chlorides, [Th(NpO2)6(H2O)8(OH)Cl9]·H2O and [Th(NpO2)6(H2O)9Cl9]Cl. Radiochemistry 58, 445–450 (2016). https://doi.org/10.1134/S1066362216050015

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  • DOI: https://doi.org/10.1134/S1066362216050015

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