The structure of dinuclear fluorooxalatouranylates Rb5[(UO2)2(C2O4)4F] · 2H2O and Ba5[(UO2)2(C2O4)4F]2 · 22H2O

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Abstract

Using X-ray diffraction analysis, the structure of the first obtained crystals of Rb5[(UO2)2(C2O4)4F] · 2H2O (I) and Ba5[(UO2)2(C2O4)4F]2 · 22H2O (II) was studied (CCDC № 2392480 (I), 2392481 (II)). The uranium-containing structural units are dinuclear complexes of the same composition [(UO2)2(C2O4)4F]5−, but different structure, which is described by the crystallochemical formulas: A2T11B013M1 (I) and A2B014M2 (II), where A = UO22+, T11 or B01 = C2O42−, and M1 or M2 = F−. The complexes contain crystallographically nonequivalent U(VI) atoms, which are part of uranyl ions and implement pentagonal-bipyramidal coordination. In I, the U(VI) atoms form coordination polyhedra UO2FO4 and UO2O5, and in II — only UO2FO4. In both structures, the dinuclear complexes [(UO2)2(C2O4)4F]5− are connected to form a 3D framework due to the coordination bonds R-O and R-F (R = Rb or Ba), in the voids of which water molecules are located, participating in the formation of a set of hydrogen bonds. The obtained IR spectroscopy results for I and II are consistent with the X-ray diffraction data.

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V. N. Serezhkin

Samara National Research University

Author for correspondence.
Email: serezhkin@samsu.ru
Russian Federation, Samara

М. S. Grigoriev

Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences

Email: serezhkin@samsu.ru
Russian Federation, Moscow

М. V. Sukacheva

Samara National Research University

Email: serezhkin@samsu.ru
Russian Federation, Samara

L. B. Serezhkina

Samara National Research University

Email: serezhkin@samsu.ru
Russian Federation, Samara

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2. Fig. 1. Structure of the dinuclear complex [(UO2)2(C2O4)4F]5– with the crystal chemical formula A2T11B013M1 in structure I. The angle between adjacent uranyl ions in the complex is ≈ 47.6°.

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3. Fig. 2. Structure of crystallographically nonequivalent dinuclear complexes [(UO2)2(C2O4)4F]5– with the same crystal chemical formula A2B014M2 in structure II. The angle between adjacent uranyl ions in complex (a) is ≈ 87.4°, and in complex (b) ≈ 89.5°.

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