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 Sciences68733210.31857/S0869769825020127GEEQQWChemical SciencesХимические наукиReview ArticleStructural chemistry of tetrachloride complexes of uranyl (review)Структурная химия тетрахлоридных комплексных соединений уранила (обзор)https://orcid.org/0000-0002-8473-3580DavidovichRuven L.ДавидовичРувен Лейзерович
Russian Federation

Doctor of Sciences in Chemistry, Professor, Chief Researcher

Доктор химических наук, главный научный сотрудник, профессор

davidovich@ich.dvo.ruInstitute of Chemistry, FEB RASИнститут химии ДВО РАН0408202521561741107202511072025Copyright ©; 2025, Russian Academy of SciencesCopyright ©; 2025, Российская академия наук2025Russian Academy of SciencesРоссийская академия наукhttps://journals.eco-vector.com/0869-7698/article/view/687332

The crystal structures of tetrachloride complexes of uranyl with cations of alkali metals, and ammonium, protonated cations of organic bases, ammonium derivatives and a number of protonated organic compounds studied by single-crystal X-ray diffraction analysis are systematized and discussed. The crystal chemical features of the structure of this class of compounds have been determined. In the investigated crystal structures of UO22+ tetrachloride complexes, the coordination polyhedron of the hexavalent uranium atom has a tetragonal-bipyramidal (distorted octahedral) structure with oxygen atoms of the uranyl group located at the apical vertices of the tetragonal-bipyramidal polyhedron. The UO22+ groups in the coordination polyhedra are directed perpendicular to the equatorial plane, at the vertices of which four Cl atoms of coordinated ligands are located. In the presence in the structures of uranyl tetrachloride complexes, along with complex anions [UO2Cl4]2– and protonated cations, free Cl– ions and free, not associated with the U atom, neutral or coordinated molecules, containing acceptor atoms, the cations do not interact with the donor atoms of the Cl– anion, and form hydrogen bonds with the free chlorine ions and acceptor atoms of the free molecules. Due to the high symmetry (almost D4h) of the complex anion in the structures of tetrachloride complexes of uranyl, the compounds have been widely used for numerous physical studies, in particular spectroscopic, luminescence, functional density theory and others.

Систематизированы и обсуждены кристаллические структуры тетрахлоридных комплексных соединений уранила с катионами щелочных металлов, аммония, протонированными катионами органических оснований, производными катиона аммония и ряда протонированных органических соединений, изученных монокристальным методом рентгеноструктурного анализа. Определены кристаллохимические особенности строения данного класса соединений. В исследованных кристаллических структурах тетрахлоридных комплексных соединений UO22+ координационный полиэдр шестивалентного атома урана имеет тетрагонально-бипирамидальное (искаженное сплюснутое октаэдрическое) строение с атомами кислорода уранильной группы, расположенными в апикальных вершинах тетрагонального-бипирамидального полиэдра. Группы UO22+ в полиэдрах направлены перпендикулярно экваториальной плоскости, в вершинах которой расположены четыре атома Cl координированных лигандов. При наличии в структурах тетрахлордных комплексных соединений уранила наряду с комплексными анионами [UO2Cl4]2– и протонированными катионами свободных ионов Cl– и/или свободных, не связанных с атомом U, нейтральных или координированных молекул, содержащих акцепторные атомы, катионы не взаимодействуют с донорными атомами Cl аниона, а образуют водородные связи со свободными ионами хлора и акцепторными атомами свободных молекул. Из-за высокой симметрии (практически D4h) комплексного аниона в структурах тетрахлоридных комплексах уранила соединения широко были использованы для проведения многочисленных физических исследований, в частности спектроскопических, люминесцентных, компьютерных, теории функциональной плотности и др.

tetrachloridecomplexuranylcrystal structurecationX-ray diffraction analysisтетрахлоридкомплексуранилкристаллическая структуракатионрентгеноструктурный анализHall D., Rae A.D., Waters T.N. The Crystal Structure of Dicaesium Tetrachlorodioxouranium(VI). Acta Crystallogr.1966;20:160–162.Hall D., Rae A.D., Waters T.N. The crystal structure of dicaesium tetrachlorodioxouranium(VI) // Acta Crystallogr. 1966. Vol. 20, No. 2. P. 160–162. DOI: 10.1107/s0365110x66000355.Watkin D.J., Denning R.G., Prout K. Structure of dicaesium tetrachlorodioxouranium(VI). Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1966;47:2517–2519.Watkin D.J., Denning R.G., Prout K. Structure of dicaesium tetrachlorodioxouranium(VI) // Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1991. Vol. 47, No. 12. P. 2517–2519. DOI: 10.1107/s0108270191006777.Tutov A.G., Plakhtii V.P., Usov O.A, Bublyaev P.A., Chernenkov Yu.P. Neitronograficheskoe utochnenie struktury nelineinogo opticheskogo kristalla ditseziiuraniltetrakhlorida Cs2UO2Cl4 = [Neutron diffraction refinement of the structure of a nonlinear optical crystal dicaesiumuranyltetrachloride Cs2UO2Cl4]. Crystallographiya. 1991;36:1135–1138. (In Russ.).Тутов А.Г., Плахтий В.П., Усов О.А., Бубляев Р.А., Черненков Ю.П. Нейтронографическое уточнение структуры нелинейного оптического кристалла дицезийуранилтетрахлорида Cs2UO2Cl4 // Кристаллография. 1991. Т. 36, № 5. С. 1135–1138.Schnaars D.D., Wilson R.E. Structural and Vibrational Properties of U(VI)O2Cl42– and Pu(VI)O2Cl42– Complexes. Inorg. Chem. 1991;52:14138–14147.Schnaars D.D., Wilson R.E. Structural and Vibrational Properties of U(VI)O2Cl42– and Pu(VI)O2Cl42– Complexes // Inorg. Chem. 2013. Vol. 52. P. 14138–14147.Ohwada K. Normal coordinate analysis of dicaesium uranyl tetrachloride (Cs2UO2Cl4). Spectrochim. Acta. 1991;31A:973–977.Ohwada K. Normal coordinate analysis of dicaesium uranyl tetrachloride (Cs2UO2Cl4) // Spectrochim. Acta. 2013. Vol. 31A. P. 973–977.Ohwada K. Laser Raman Spectra and Normal Coordinate Analysis of Some Uranyl Tetrachloride Complexes. Appl. Spectr. 1980;34:327–331.Ohwada K. Laser Raman Spectra and Normal Coordinate Analysis of Some Uranyl Tetrachloride Complexes // Appl. Spectrosc. 2013. Vol. 34, No. 3. P. 327–331. DOI: 10.1366/000370280473027.Flint C.D., Tanner P.A. Luminescence and absorption spectra of M2UO2Cl4·xH2O. Molec. Phys. 1981;44:411–425.Flint C.D., Tanner P.A. Luminescence and absorption spectra of M2UO2Cl4·xH2O // Molecul. Phys. 1981. Vol. 44, No. 2. P. 411–425. DOI: 10.1080/00268978100102541.Anson C.E., Al-Jowder O., Jayasooriya U.A., Powell A.K. Dirubidium Tetrachlorodioxouranium(VI)–Water (1:2). Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1996;52:279–281.Anson C.E., Al-Jowder O., Jayasooriya U.A., Powell A.K. Dirubidium Tetrachlorodioxouranium(VI)–Water (1:2) // Acta Crystallogr. Sect. C Cryst. Struct. Commun. 1996. Vol. 52, No. 2. P. 279–281. DOI: 10.1107/s0108270195011723.Augustine L.J., Rajapaksha H., Pyrch M.M.F., Kasperski M., Forbes T.Z., Mason S.E. Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engagedin Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses. Inorg. Chem. 2023;62:372–380.Augustine L.J., Rajapaksha H., Pyrch M.M.F., Kasperski M., Forbes T.Z., Mason S.E. Periodic Density Functional Theory Calculations of Uranyl Tetrachloride Compounds Engaged in Uranyl–Cation and Uranyl–Hydrogen Interactions: Electronic Structure, Vibrational, and Thermodynamic Analyses // Inorg. Chem. 2023. Vol. 62. P. 372–380.Kohlgruber T.A., Surbella III R.G. (NH4)2[UO2Cl4]·2H2O, a new uranyl tetrachloride with ammonium charge-balancing cations. Acta Crystallogr. 2023;E79:702–706.Kohlgruber T.A., Surbella III R.G. (NH4)2[UO2Cl4]·2H2O, a new uranyl tetrachloride with ammonium charge-balancing cations // Acta Crystallogr. 2023. Vol. E79, No. 8. P. 702–706. https://doi.org/10.1107/S2056989023005753.Di Sipio L., Tondello E., Pelizzi G., Ingletto G., Montenero A. Di-(Tetramethyl)ammonium Uranyl Tetrahalides [(CH3)4N]2UO2Cl4, [(CH3)4N]2UO2Br4. Cryst. Struct. Comm. 1974;3:297–300.Di Sipio L., Tondello E., Pelizzi G., Ingletto G., Montenero A. Di-(Tetramethyl)ammonium Uranyl Tetrahalides [(CH3)4N]2UO2Cl4, [(CH3)4N]2UO2Br4 // Cryst. Struct. Commun. 1974. Vol. 3. P. 297–300.Bois C., Dao N.Q., Rodier N. Refinement of the crystal structure of the bis(triethylammonium) tetrachlorodioxouranium(VI). J. Inorg. Nucl. Chem. 1976;38:755–757.Bois C., Dao N.Q., Rodier N. Refinement of the crystal structure of the bis(triethylammonium) tetrachlorodioxouranium(VI) // J. Inorg. Nucl. Chem. 1976. Vol. 38. P. 755–757.Bois C., Dao N.Q., Rodier N. Structure Cristalline de Bis(tétraéthylammonium) Tétrachlorodioxouranium(VI). Acta Crystallogr. 1976;B32:1541–1544.Bois C., Dao N.Q., Rodier N. Structure Cristalline de Bis(tétraéthylammonium) Tétrachlorodioxouranium(VI) // Acta Crystallogr. 1976. Vol. B32. P. 1541–1544.Di Sipio L., Tondello E., Pelizzi G., Ingletto G., Montenero A. Di-(Tetrapropylammonium) Uranyl Tetrachloride [(CH3)(CH2)(CH2)4N]2UO2Cl4. Cryst. Struct. Comm. 1974;3:731–734Di Sipio L., Tondello E., Pelizzi G., Ingletto G., Montenero A. Di-(Tetrapropylammonium) Uranyl Tetrachloride [(CH3)(CH2)(CH2)4N]2UO2Cl4 // Cryst. Struct. Commun. 1974. Vol. 3. P. 731–734.Di Sipio L., Tondello E., Pelizzi G., Ingletto G., Montenero A. Di-(Tetrabutylammonium) Uranyl Tetrachloride [(CH3)(CH2)3)4N]2UO2Cl4. Cryst. Struct. Comm. 1974;3:527–530.Di Sipio L., Tondello E., Pelizzi G., Ingletto G., Montenero A. Di- (Tetrabutylammonium) Uranyl Tetrachloride [(CH3)(CH2)3)4N]2UO2Cl4 // Cryst. Struct. Commun. 1974. Vol. 3. P. 527–530.Di Sipio L., Pasquetto A., Pelizzi G., Ingletto G., Montenero A. DI (1,10 H-Phenanthrolinium) Tetrachlorodioxouranate, (C12H9N2)2UO2Cl4. Cryst. Struct. Comm. 1981;10:1153–1157.Di Sipio L., Pasquetto A., Pelizzi G., Ingletto G., Montenero A. DI (1,10 H-Phenanthrolinium) Tetrachlorodioxouranate, (C12H9N2)2UO2Cl4 // Cryst. Struct. Commun. 1980. Vol. 10. P. 1153–1157.Perry D.L., Freyberg D.P., Zalkin A. Imidazolium tetrachlorodioxouranate(VI), [C3N2H5]2[UO2Cl4]2–. J. Inorg. Nucl. Chem. 1980;42:243–245.Perry D.L., Freyberg D.P., Zalkin A. Imidazolium tetrachlorodioxouranate(VI), [C3N2H5]2[UO2Cl4]2– // J. Inorg. Nucl. Chem. 1980. Vol. 42, No. 2. P. 243–245. DOI: 10.1016/0022-1902(80)80248-x.Zalkin A., Perry D., Tsao L., Zhang D. Bis(2-methylimidazolium) Tetrachlorodioxouranate(VI), 2C4H7N2+.UCI4O22–. Acta Crystallogr. 1983;C39:1186–1189.Zalkin A., Perry D., Tsao L., Zhang D. Bis(2-methylimidazolium) Tetrachlorodioxouranate(VI), 2C4H7N2+.UCI4O22– // Acta Crystallogr. 1983. Vol. C39. P. 1186–1189.Deifel N.P., Cahill C.L. The uranyl tetrachloride anion as a tecton in the assembly of U(VI) hybrid materials. CrystEngComm. 2009;11:2739–2744.Deifel N.P., Cahill C.L. The uranyl tetrachloride anion as a tecton in the assembly of U(VI) hybrid materials // CrystEngComm. 2009. Vol. 11. P. 2739–2744.Pyrch M.M., Williams J.M., Kasperski M.W, Applegate L.C., Forbes T.Z. Synthesis and spectroscopic characterization of actinyl(VI) tetrahalidecoordination compounds containing 2,2′-bipyridine. Inorg. Chim. Acta. 2020;508. 119628.Pyrch M.M., Williams J.M., Kasperski M.W., Applegate L.C., Forbes T.Z. Synthesis and spectroscopic characterization of actinyl(VI) tetrahalidecoordination compounds containing 2,2′-bipyridine // Inorg. Chim. Acta. 2020. Vol. 508. 119628.Surbella III R.G., Andrews M.B., Cahill C.L. Self-assembly of [UO2X4]2– (X¼Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties. J. Solid. State. Chem. 2016;236:257–271.Surbella III R.G., Andrews M.B., Cahill C.L. Self-assembly of [UO2X4]2– (X¼Cl, Br) dianions with γ substituted pyridinium cations: Structural systematics and fluorescence properties // J. Solid State Chem. 2016. Vol. 236. P. 257–271.Bombieri G., Forsellini G., Graziani R. Structure of Bis(2-pyridylthio-2-pyridinium) Tetrachlorodioxouranate(Vl). Acta Crystallogr. 1978;B34:2622–2624.Bombieri G., Forsellini G., Graziani R. Structure of Bis(2-pyridylthio-2-pyridinium) Tetrachlorodioxouranate(Vl) // Acta Crystallogr. 1978. Vol. B34. P. 2622–2624.Schnaars D.D., Wilson R.E. Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO2Cl42–. Inorg. Chem. 2014;53:11036–11045.Schnaars D.D., Wilson R.E. Lattice Solvent and Crystal Phase Effects on the Vibrational Spectra of UO2Cl42– // Inorg. Chem. 2014. Vol. 53. 11036.Lhoste J., Henry N., Loiseau T., Guyot T., Abraham F. Crystal structures of 2,2′:6′,2″-terpyridine uranyl chlorides molecular assemblies and their luminescence signatures. Polyhedron. 2013;50:321–327.Lhoste J., Henry N., Loiseau T., Guyot T., Abraham F. Crystal structures of 2,2′:6′,2″-terpyridine uranyl chlorides molecular assemblies and their luminescence signatures // Polyhedron. 2013. Vol. 50. P. 321–327.Hashem E., Swinburne A.N., Schulzke C., Evans R.C., Platts J.A, Kerridge A., Natrajan L.S., Baker R.J. Emission spectroscopy of uranium(IV) compounds: a combined synthetic, spectroscopic and computational study. RSC Advances. 2013;3:4350–4361.Hashem E., Swinburne A.N., Schulzke C., Evans R.C., Platts J.A., Kerridge A., Natrajan L.S., Baker R.J. Emission spectroscopy of uranium(IV) compounds: a combined synthetic, spectroscopic and computational study // RSC Advances. 2013. Vol. 3. P. 4350–4361.Prasad N., Govil G. Study of geometrical parameters in N-H...N type of hydrogen Bonds. Proc. Indian Acad. Sci (Chem. Sci.).1980;89:253–262.Prasad N., Govil G. Study of geometrical parameters in N–H...N type of hydrogen Bonds // Proc. Indian Acad. Sci. (Chem. Sci.). 1980. Vol. 89. P. 253–262.Pospieszna I., Radecka-Paryzek W., Kubicki M. Bis(pyridinium) trans- tetrachloridodioxidouranate(VI) dioxane solvate. Acta Crystallogr. 2008;E64. m239.Pospieszna I., Radecka-Paryzek W., Kubicki M. Bis(pyridinium)trans-tetrachloridodioxidouranate(VI) dioxane solvate //Acta Crystallogr. 2008. Vol. E64. m239. DOI: 10.1107/S1600536807066949.