Vestnik of the Far East Branch of the Russian Academy of SciencesVestnik of the Far East Branch of the Russian Academy of SciencesВестник Дальневосточного отделения Российской академии наук0869-7698The Russian Academy of Sciences68894210.31857/S0869769825030158POENGQChemical SciencesХимические наукиResearch ArticleStructural chemistry of UO₂Cl₂ complexes with neutral donor ligands (review)Структурная химия комплексных соединений UO₂Cl₂ с нейтральными донорными лигандами (обзор)https://orcid.org/0000-0002-8473-3580DavidovichRuven L.ДавидовичРувен Лейзерович
Russian Federation

Doctor of Sciences in Chemistry, Chief Researcher, Professor

доктор химических наук, главный научный сотрудник, профессор

davidovich@ich.dvo.ruInstitute of Chemistry, FEB RASИнститут химии ДВО РАН0409202531701931008202510082025Copyright ©; 2025, Russian Academy of SciencesCopyright ©; 2025, Российская академия наук2025Russian Academy of SciencesРоссийская академия наукhttps://journals.eco-vector.com/0869-7698/article/view/688942

The crystal structures of UO2Cl2 complexes with neutral ligands, containing O, N, S and C donor atoms, studied by single-crystal X-ray diffraction analysis have been systematized and discussed. The crystal chemical features of the structure of mixed-ligand complexes UO2Cl2Ln were determined depending on the ratio of the number of Cl atoms to the number of donor atoms O, N, S and C of coordinated ligands in the compound. In the mixed-ligand complexes UO2Cl2Ln at the ratios 2Cl : O, 2Cl : 3O(N) and Cl : 4O, the coordination polyhedron of the hexavalent uranium atom in the structure has a pentagonal-bipyramidal structure. The oxygen atoms of the uranyl group are located on the vertical axis of the pentagonal bipyramid, perpendicular to the equatorial plane of the polyhedron, in which five atoms of coordinated ligands are located. At the ratio 2Cl : 2O (N, S, C) in mixed-ligand complexes UO2Cl2Ln uranium atoms form tetragonal bipyramidal polyhedra (distorted octahedra) with uranyl groups in the axial vertices, chlorine atoms and donor ligand atoms in the equatorial plane. In a small group of mixed-ligand compounds UO2Cl2Ln with a 2Cl : 4N ratio, hexagonal-bipyramidal polyhedra of U atoms with Cl and N atoms in the equatorial plane and a nonlinear group UO22+ (∠ O(1)=U=O(2) 161.81(11)–168.3(3)°) was established.

Систематизированы и обсуждены кристаллические структуры комплексных соединений UO2Cl2 с нейтральными лигандами, содержащими донорные атомы O, N, S и C, изученных монокристальным методом рентгеноструктурного анализа. Определены кристаллохимические особенности строения разнолигандных комплексных соединений UO2Cl2Ln в зависимости от отношения числа атомов Cl к числу донорных атомов O, N, S и C координированных лигандов в соединении. В разнолигандных комплексных соединениях UO2Cl2Ln при отношении 2Cl : O, 2Cl : 3O(N) и Cl : 4O координационный полиэдр шестивалентного атома урана в структуре имеет пентагонально-бипирамидальное строение. Атомы кислорода уранильной группы сосредоточены на вертикальной оси пентагональной бипирамиды, перпендикулярно экваториальной плоскости полиэдра, в которой расположены пять атомов координированных лигандов. При отношении 2Cl : 2O (N, S, C) в разнолигандных комплексных соединениях UO2Cl2Ln атомы урана образуют тетрагонально-бипирамидальные полиэдры (искаженные октаэдры) с уранильными группами в аксиальных вершинах, атомами хлора и донорными атомами лигандов в экваториальной плоскости. В небольшой группе разнолигандных соединений UO2Cl2Ln с отношением 2Cl : 4N реализуются гексагонально-биирамидальные полиэдры атомов U с атомами Cl и N в экваториальной плоскости и нелинейной группой UO22+ (∠ O(1)=U=O(2) 161.81(11)–168.3(3)°).

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