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Synthesis and structure of crystalline complexes of Np(V) with isophthalic acid. Cation-cation interaction in the compounds [(NpO2)2(C6H4(COO)2)(H2O)]·H2O and M[(NpO2)(C6H4(COO)2)]·2.5H2O, M = [H3O], [NH4], and [C(NH2)3]

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Abstract

New Np(V) isophthalate complexes of the compositions [(NpO2)2(C6H4(COO)2)(H2O)]·H2O (I) and M[(NpO2)(C6H4(COO)2)]·nH2O, where M = [H3O] (IIa), [NH4] (IIb), and [C(NH2)3] (IIc), were synthesized and studied by single crystal X-ray diffraction. Cation-cation interaction was revealed in their structure. In the structure of I, each of three nonequivalent NpO2 groups is a bidentate ligand and simultaneously coordinates two adjacent neptunyl(V) ions to form “square” cationic networks. The cationic networks in the crystal are linked by bridging [C6H4(COO)2]2− anions exhibiting the coordination capacity equal to 5. Three independent Np atoms are characterized by different shapes of the coordination polyhedron (CP): hexagonal, pentagonal, and tetragonal bipyramids. Tetrameric cationic complexes in which each NpO2 group is a monodentate ligand and a coordination center for the adjacent group are formed in the structure of II. The cationic complexes are linked by the bridging [C6H4(COO)2]2− anions whose coordination capacity is 4; the CPs of the Np atoms are pentagonal bipyramids. In the structure of II, replacement of relatively small outer-sphere hydroxonium and ammonium cations by guanidinium cation does not alter the overall structural motif of the crystal.

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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

    M. S. Grigor’ev, I. A. Charushnikova & A. M. Fedoseev

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  1. M. S. Grigor’ev
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  2. I. A. Charushnikova
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  3. A. M. Fedoseev
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Correspondence to I. A. Charushnikova.

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Original Russian Text © M.S. Grigor’ev, I.A. Charushnikova, A.M. Fedoseev, 2015, published in Radiokhimiya, 2015, Vol. 57, No. 4, pp. 329–336.

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Grigor’ev, M.S., Charushnikova, I.A. & Fedoseev, A.M. Synthesis and structure of crystalline complexes of Np(V) with isophthalic acid. Cation-cation interaction in the compounds [(NpO2)2(C6H4(COO)2)(H2O)]·H2O and M[(NpO2)(C6H4(COO)2)]·2.5H2O, M = [H3O], [NH4], and [C(NH2)3]. Radiochemistry 57, 386–394 (2015). https://doi.org/10.1134/S1066362215040086

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  • DOI: https://doi.org/10.1134/S1066362215040086

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