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Synthesis and Structure of Uranyl Succinate Complex with Isonicotinic Acid and New Polymorph of Uranyl Succinate Monohydrate

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Abstract

Synthesis, IR spectroscopic and X-ray structural studies of crystals [UO2(C4H4O4)(C6H5NO2)2] (I) and a new modification [UO2(C4H4O4)(H2O)] (II), where C4H4O42– are succinate ions, and C6H5NO2 is isonicotinic acid. Structure I is formed by chains in which succinate ions play the role of bridging ligands Q02 and B2, and isonicotinic acid molecules in the form of a zwitterion are monodentate ligands M1. Chains I correspond to the crystal chemical formula АQ020.5B20.5M12, where = UO22+, Q02 and B2 = C4H4O42–, and M1 = C6H5NO2. The reasons of the change in the coordination type of half of the succinate ions in I from characteristic Q02 to rare B2 are explained from the standpoint of the 18-electron rule in uranyl compounds. Structure II, like the two already known modifications, corresponds to the crystal chemical formula АQ4M1, where A = UO22+, Q4 = C4H4O42–, and M1 = H2O. By the example of uranyl succinate monohydrate polymorphs, it was found that, like silica polymorphs, chemically identical 3D uranyl-containing frameworks can differ both in topology (reconstructive isomers) and in the symmetry of the framework (deformation isomers). It was found that the new γ-form of II in the region of ≈180 K reversibly transforms into the already known low-temperature β-modification. It was shown using the Voronoi–Dirichlet polyhedra, that the available data for the fourth polymorph [UO2(C4H4O4)(H2O)] registered in the CSD as {SUCCUR02}, are erroneous.

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Funding

X-ray diffraction experiments were carried out at the Center for Collective Use of the PMI IPCE RAS with partial funding from the Ministry of Science and Higher Education of the Russian Federation (topic N AAAA-A18-118040590105-4). One of the co-authors (EFR) is grateful to the Russian Science Foundation for financial support (project no. 20-73-10250).

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Authors and Affiliations

  1. Samara National Research University, 443011, Samara, Russia

    L. B. Serezhkina, E. F. Rogaleva & V. N. Serezhkin

  2. Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, 119071, Moscow, Russia

    M. S. Grigoriev

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  1. L. B. Serezhkina
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Correspondence to L. B. Serezhkina.

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Translated from Radiokhimiya, No. 4, pp. 337–348, April, 2021 https://doi.org/10.31857/S0033831121040055

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Serezhkina, L.B., Grigoriev, M.S., Rogaleva, E.F. et al. Synthesis and Structure of Uranyl Succinate Complex with Isonicotinic Acid and New Polymorph of Uranyl Succinate Monohydrate. Radiochemistry 63, 428–438 (2021). https://doi.org/10.1134/S1066362221040056

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