Crystal structures of non-centrosymmetric fluorouranylates Na3[UO2F5] and CaRb4[UO2F4]3⋅3H2O
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Viktor N. Serezhkin
,
Mikhail S. Grigoriev
,
Marina V. Sukacheva
Abstract
The structure of Na3[UO2F5] (I) and CaRb4[UO2F4]3⋅3H2O (II) crystals was studied using X-ray diffraction analysis. The uranium-containing structural units are pentagonal bipyramids [UO2F5]3−, which are isolated from each other in I and linked by bridging fluorine atoms into trinuclear complexes of the composition [(UO2)3F12]6− in II. The latter one fills the existing gap in the crystal chemistry of uranyl fluorides and oxofluorides by representing the first example of a trinuclear complex, while di-, tetra- and pentanuclear complexes have been observed before. The first compound has been known for more than half a century, although here we present the first report on its crystal structure. The crystal chemical formulae of the uranium-containing complexes in I and II are AM 1 5 and A3M 2 3M 1 9, where A = UO22+, М2 and М1 = F−. In both structures, the uranyl-containing complexes are linked into 3D frameworks by R–F and R–O coordination bonds with outer-sphere R cations (R = Na, Rb or Ca). As both compounds I and II turned out to be non-centrosymmetric their ability to generate the second harmonic was theoretically predicted based on parameters of Voronoi–Dirichlet polyhedra. Experimental verification of the obtained values is of undoubted interest.
Funding source: Russian Science Foundation
Award Identifier / Grant number: 20-73-10250
Funding source: Ministry of Science and Higher Education of the Russian Federation
Award Identifier / Grant number: FSSS-2024-0016
Acknowledgements
X-ray diffraction experiments were performed at the Center for Shared Use of Physical Methods of Investigation at the Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences.
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Research ethics: Not applicable.
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Informed consent: Not applicable.
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Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.
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Use of Large Language Models, AI and Machine Learning Tools: None declared.
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Conflict of interest: The authors state no conflict of interest.
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Research funding: The study was funded by a grant of the Russian Science Foundation (project number 20-73-10250, https://rscf.ru/en/project/20-73-10250/). Estimation of nonlinear optical activity was performed within the State assignment for scientific research to Samara University (project FSSS-2024-0016).
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Data availability: Not applicable.
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