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Title: Synthesis and crystal structure analysis of uranyl triple acetates

Abstract

Single crystals of triple acetates NaR[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O (R=Mg, Co, Ni, Zn), well-known for their use as reagents for sodium determination, were grown from aqueous solutions and their structural and spectroscopic properties were studied. Crystal structures of the mentioned phases are based upon (Na[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}){sup 2–} clusters and [R(H{sub 2}O){sub 6}]{sup 2+} aqua-complexes. The cooling of a single crystal of NaMg[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O from 300 to 100 K leads to a phase transition from trigonal to monoclinic crystal system. Intermolecular interactions between the structural units and their mutual packing were studied and compared from the point of view of the stereoatomic model of crystal structures based on Voronoi-Dirichlet tessellation. Using this method we compared the crystal structures of the triple acetates with Na[UO{sub 2}(CH{sub 3}COO){sub 3}] and [R(H{sub 2}O){sub 6}][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} and proposed reasons of triple acetates stability. Infrared and Raman spectra were collected and their bands were assigned. - Graphical abstract: Single crystals of uranium based triple acetates, analytical reagents for sodium determination, were synthesized and structurally, spectroscopically and topologically characterized. The structures were compared with the structures of compounds from preceding families [M(H{sub 2}O){sub 6})][UO{sub 2}(CH{submore » 3}COO){sub 3}]{sub 2} (M = Mg, Co, Ni, Zn) and Na[UO{sub 2}(CH{sub 3}COO){sub 3}]. Analysis was performed with the method of molecular Voronoi-Dirichlet polyhedra to reveal a large contribution of the hydrogen bonds into intermolecular interactions which can be a reason of low solubility of studied complexes.« less

Authors:
 [1];  [2]; ;  [3];  [1];  [4]
  1. Institute for Energy and Climate Research (IEK-6), Forschungszentrum Jülich GmbH, 52428 Jülich (Germany)
  2. (Russian Federation)
  3. Department of Chemistry, Samara National Research University, 443086 Samara (Russian Federation)
  4. (Germany)
Publication Date:
OSTI Identifier:
22658126
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 244; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; ACETATES; AQUEOUS SOLUTIONS; COBALT COMPOUNDS; CRYSTAL STRUCTURE; CRYSTALLIZATION; EXPERIMENTAL DATA; MAGNESIUM COMPOUNDS; MONOCLINIC LATTICES; MONOCRYSTALS; NICKEL COMPOUNDS; RAMAN SPECTRA; RAMAN SPECTROSCOPY; SODIUM COMPOUNDS; SYNTHESIS; URANIUM DIOXIDE; ZINC COMPOUNDS

Citation Formats

Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com, Department of Chemistry, Samara National Research University, 443086 Samara, Serezhkina, Larisa B., Serezhkin, Victor N., Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de, and Institut für Kristallographie, RWTH Aachen University, 52066 Aachen. Synthesis and crystal structure analysis of uranyl triple acetates. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.09.019.
Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com, Department of Chemistry, Samara National Research University, 443086 Samara, Serezhkina, Larisa B., Serezhkin, Victor N., Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de, & Institut für Kristallographie, RWTH Aachen University, 52066 Aachen. Synthesis and crystal structure analysis of uranyl triple acetates. United States. doi:10.1016/J.JSSC.2016.09.019.
Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com, Department of Chemistry, Samara National Research University, 443086 Samara, Serezhkina, Larisa B., Serezhkin, Victor N., Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de, and Institut für Kristallographie, RWTH Aachen University, 52066 Aachen. Thu . "Synthesis and crystal structure analysis of uranyl triple acetates". United States. doi:10.1016/J.JSSC.2016.09.019.
@article{osti_22658126,
title = {Synthesis and crystal structure analysis of uranyl triple acetates},
author = {Klepov, Vladislav V., E-mail: vladislavklepov@gmail.com and Department of Chemistry, Samara National Research University, 443086 Samara and Serezhkina, Larisa B. and Serezhkin, Victor N. and Alekseev, Evgeny V., E-mail: e.alekseev@fz-juelich.de and Institut für Kristallographie, RWTH Aachen University, 52066 Aachen},
abstractNote = {Single crystals of triple acetates NaR[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O (R=Mg, Co, Ni, Zn), well-known for their use as reagents for sodium determination, were grown from aqueous solutions and their structural and spectroscopic properties were studied. Crystal structures of the mentioned phases are based upon (Na[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}){sup 2–} clusters and [R(H{sub 2}O){sub 6}]{sup 2+} aqua-complexes. The cooling of a single crystal of NaMg[UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 3}·6H{sub 2}O from 300 to 100 K leads to a phase transition from trigonal to monoclinic crystal system. Intermolecular interactions between the structural units and their mutual packing were studied and compared from the point of view of the stereoatomic model of crystal structures based on Voronoi-Dirichlet tessellation. Using this method we compared the crystal structures of the triple acetates with Na[UO{sub 2}(CH{sub 3}COO){sub 3}] and [R(H{sub 2}O){sub 6}][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} and proposed reasons of triple acetates stability. Infrared and Raman spectra were collected and their bands were assigned. - Graphical abstract: Single crystals of uranium based triple acetates, analytical reagents for sodium determination, were synthesized and structurally, spectroscopically and topologically characterized. The structures were compared with the structures of compounds from preceding families [M(H{sub 2}O){sub 6})][UO{sub 2}(CH{sub 3}COO){sub 3}]{sub 2} (M = Mg, Co, Ni, Zn) and Na[UO{sub 2}(CH{sub 3}COO){sub 3}]. Analysis was performed with the method of molecular Voronoi-Dirichlet polyhedra to reveal a large contribution of the hydrogen bonds into intermolecular interactions which can be a reason of low solubility of studied complexes.},
doi = {10.1016/J.JSSC.2016.09.019},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 244,
place = {United States},
year = {2016},
month = {12}
}