Alkaline Metal Fluoroxalatouranylates: Structure and Some Properties
- Authors: Serezhkin V.N.1, Grigoriev М.S.2, Sukacheva М.V.1, Losev V.Y.1, Serezhkina L.B.1
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Affiliations:
- Samara National Research University
- Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences
- Issue: Vol 69, No 2 (2024)
- Pages: 183-192
- Section: КООРДИНАЦИОННЫЕ СОЕДИНЕНИЯ
- URL: https://journals.rcsi.science/0044-457X/article/view/260614
- DOI: https://doi.org/10.31857/S0044457X24020054
- EDN: https://elibrary.ru/ZHSYUR
- ID: 260614
Cite item
Abstract
Crystal structure Na3[UO2(C2O4)F3] · 4H2O (I), K3[UO2(C2O4)F3] (II), K3[UO2(C2O4)2F] · 3H2O (III) and Cs[UO2(C2O4)F] · H2O (IV) first studied by X-ray diffraction. Uranium–containing structural units are complexes [UO2(C2O4)F3]3ˉ (for I and II), [UO2(C2O4)2F]3- (III) and [UO2(C2O4)F]- (IV), accordingly with crystal chemical formulas А(В01)M13, А(В01)2M1 and А(Q02)M1, where A = UO22+, B01 or Q02 = C2O42-, and M1 = F- . In all compounds U(VI) atoms implement pentagonal-bipyramidal coordination, at that in I—III uranyl complexes have single–core structure, and in IV crystals–chain structure which is similar for the well — known for [UO2(C2O4)(H2O)] · 2H2O. The obtained results suggest that a sharp increase in the solubility of uranyl oxalate trihydrate in aqueous solutions with the addition of fluorides is due to the well-known effect of structural depolymerization of coordination polymers of d- or f-metals in the presence of fluoride ions. Semi-empirical calculation and comparison of calculated and experimental oscillation frequencies in IR spectra II and IV are carried out.
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About the authors
V. N. Serezhkin
Samara National Research University
Author for correspondence.
Email: serezhkin@samsu.ru
Russian Federation, Samara, 443011
М. S. Grigoriev
Frumkin Institute of Physical Chemistry and Electrochemistry of the Russian Academy of Sciences
Email: serezhkin@samsu.ru
Russian Federation, Moscow, 119071
М. V. Sukacheva
Samara National Research University
Email: serezhkin@samsu.ru
Russian Federation, Samara, 443011
V. Y. Losev
Samara National Research University
Email: serezhkin@samsu.ru
Russian Federation, Samara, 443011
L. B. Serezhkina
Samara National Research University
Email: serezhkin@samsu.ru
Russian Federation, Samara, 443011
References
- Chernyaev I.I. Complex Compounds of Uranium. New York: Daniel Devy and Co. Inc., 1966.
- Щелоков Р.Н. // Химия платиновых и тяжелых металлов / Под ред. Щелокова Р.Н. М.: Наука, 1975. С. 110.
- Михайлов Ю.Н. // Химия платиновых и тяжелых металлов / Под ред. Щелокова Р.Н. М.: Наука, 1975. С. 127.
- Давидович Р.Л. // Вестник ДВО РАН. 2022. № 6. C. 5.
- Inorganic crystal structure database. Gmelin-institut fur Anoranische Chemie & FIC Karlsruhe, 2022.
- Cambridge structural database system. Cambridge Crystallographic Data Centre, 2022.
- Serezhkin V.N., Pushkin D.V., Serezhkina L.B. // Radiochemistry. 2022. V. 64. № 4. P. 491.
- Zachariasen W.H. // Acta Crystallogr. 1948. V. 1. P. 277.
- Kim J.-Y., Norquist A.J., O‘Hare D. // Dalton Trans. 2003. P. 2813. https://doi.org/10.1039/B30673
- Deifel N.P., Holman K.T., Cahill C.L. // Chem. Commun. 2008. P. 6037.
- Nguyen Quy Dao, Bkouche-Waksman I., Walewski M., Caceres D. // Bull. Soc. Chim. Fr. 1984. P. 129.
- Матюха В.А., Матюха С.В. Оксалаты редкоземельных элементов и актиноидов. М.: Энергоатомиздат, 2004. 408 с.
- Черняев И.И., Головня В.А., Щелоков Р.Н. // Журн. неорган. химии. 1961. Т. 6. С. 557.
- SAINT-Plus (Version 7.68). Bruker AXS Inc., Madison, Wisconsin, USA. 2007.
- Krause L., Herbst-Irmer R., Sheldrick G.M., Stalke D. // J. Appl. Cryst. 2015. V. 48. Part 1. P. 3.
- TWINABS (Version 2012/1). Madison: Bruker AXS Inc., 2012.
- Sheldrick G.M. // Acta Crystallogr. 2008. V. 64A. № 1. P. 112. https://doi.org/
- Sheldrick G.M. // Acta Crystallogr. 2015. V. 71C. № 1. P. 3. https://doi.org/10.1107/ S2053229614024218
- Cережкин В.Н., Михайлов Ю.Н., Буслаев Ю.А. // Журн. неорган. химии. 1997. Т. 42. № 12. С. 2036.
- Serezhkin V.N., Vologzhanina A.V., Serezhkina L.B. et al. // Acta Crystallogr. 2009. V. 65B. Part 1. P. 45. https://doi.org/10.1107/S0108768108038846
- Serezhkin V.N., Verevkin A.G., Smirnov O.P., Plakhtii V.P. // Russ. J. Inorg. Chem. 2010. V. 55. № 10. Р. 1600.
- Serezhkin V.N., Neklyudova N.A., Smirnov O.P. // Russ. J. Inorg. Chem. 2012. V. 57. № 6. Р. 864.
- Jayadevan N.C., Chackraburtty D.M. // Acta Crystallogr. 1972. V. 28 B. P. 3178.
- Михайлов Ю.Н., Горбунова Ю.E., Шишкина O.В. и др. // Журн. неорган. химии. 1999. Т. 44. № 9. С. 1448.
- Giesting O.A., Porter N.J., Burns P.C. // Z. Kristallogr. 2006. V. 221. № 4. P. 252.
- Артемьева М.Ю., Сережкин В.Н., Смирнов O.Н., Плахтий В.П. // Журн. неорган. химии. 2006. Т. 51. № 8. С. 1392.
- Давидович Р.Л. // Коорд. химия. 1986. Т. 12. № 2. С. 281.
- Давидович Р.Л. // Вестник ДВО РАН. 2022. № 2. С. 49. https://doi.org/10.37102/0869-7698_2022_222_02_4
- Сережкина Л.Б., Сережкин В.Н., Пушкин Д.В., Лосев В.Ю. Колебательная спектроскопия неорганических соединений. Самара: Самарский университет, 2009. 132 с.
- Грибов Л.А., Дементьев В.А. Методы и алгоритмы вычислений в теории колебательных спектров молекул. М.: Наука, 1981. 356 с.
- Nakamoto K. Infrared and Raman Spectra of Inorganic and Coordination Compounds. New Jersey: John Wiley & Sons. Inc., 2009. Part B. 419 p.
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