skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Potassium and magnesium succinatouranilates – Synthesis and crystal structure

Abstract

Single crystal X-ray diffraction has been applied to determine the structures of two new uranyl coordination polymers: K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}] [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), where C{sub 4}H{sub 4}O{sub 4}{sup 2-} is succinate anion. Crystals of 1 and 2 contain polymeric complex anions [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} with the same A{sub 2}Q{sup 02}{sub 3} crystallochemical formula (A=UO{sub 2}{sup 2+}, Q{sup 02}=C{sub 4}O{sub 4}H{sub 4}{sup 2-}), and have layered (1) or chain (2) structure. It has been found, that conformation of succinate ions is one of the factors, which affects the structure of [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} anions. IR spectra of these new compounds are in good agreement with crystallographic data. Topological analysis of the uranium dicarboxylates with A{sub 2}Q{sup 02}{sub 3} crystallochemical formula has shown the presence of five isomers which differ from each other in coordination sequences and / or dimensionality. - Graphical abstract: Crystal structures of two new uranium(VI) coordination polymers with succinate linkers, namely K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}][(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2),more » were determined by single-crystal XRD. Crystals of studied compounds are based on 2D or 1D structural units with the same composition and crystallochemical formula. Topological isomerism in A{sub 2}Q{sup 02}{sub 3} crystallochemical group and conformations of succinate anions in uranyl complexes are under discussion. - Highlights: • Two new uranium coordination polymers were synthesized. • Their structural units have the same composition and crystallochemical formula. • In spite the same composition and CCF dimensionality of units is different. • Structural features of uranyl CPs are affected by linker conformations.« less

Authors:
 [1];  [2]; ;  [1]
  1. Samara National Research University, 443086 Samara (Russian Federation)
  2. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, 119071 Moscow (Russian Federation)
Publication Date:
OSTI Identifier:
22658251
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 248; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; CRYSTAL STRUCTURE; EXPERIMENTAL DATA; INFRARED SPECTRA; MONOCRYSTALS; POLYMERIZATION; POLYMERS; SYNTHESIS; URANIUM DIOXIDE; URANYL COMPLEXES; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Novikov, S.A., E-mail: serg.alex.novikov@gmail.com, Grigoriev, M.S., Serezhkina, L.B., and Serezhkin, V.N. Potassium and magnesium succinatouranilates – Synthesis and crystal structure. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2017.02.010.
Novikov, S.A., E-mail: serg.alex.novikov@gmail.com, Grigoriev, M.S., Serezhkina, L.B., & Serezhkin, V.N. Potassium and magnesium succinatouranilates – Synthesis and crystal structure. United States. doi:10.1016/J.JSSC.2017.02.010.
Novikov, S.A., E-mail: serg.alex.novikov@gmail.com, Grigoriev, M.S., Serezhkina, L.B., and Serezhkin, V.N. Sat . "Potassium and magnesium succinatouranilates – Synthesis and crystal structure". United States. doi:10.1016/J.JSSC.2017.02.010.
@article{osti_22658251,
title = {Potassium and magnesium succinatouranilates – Synthesis and crystal structure},
author = {Novikov, S.A., E-mail: serg.alex.novikov@gmail.com and Grigoriev, M.S. and Serezhkina, L.B. and Serezhkin, V.N.},
abstractNote = {Single crystal X-ray diffraction has been applied to determine the structures of two new uranyl coordination polymers: K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}] [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), where C{sub 4}H{sub 4}O{sub 4}{sup 2-} is succinate anion. Crystals of 1 and 2 contain polymeric complex anions [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} with the same A{sub 2}Q{sup 02}{sub 3} crystallochemical formula (A=UO{sub 2}{sup 2+}, Q{sup 02}=C{sub 4}O{sub 4}H{sub 4}{sup 2-}), and have layered (1) or chain (2) structure. It has been found, that conformation of succinate ions is one of the factors, which affects the structure of [(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]{sup 2-} anions. IR spectra of these new compounds are in good agreement with crystallographic data. Topological analysis of the uranium dicarboxylates with A{sub 2}Q{sup 02}{sub 3} crystallochemical formula has shown the presence of five isomers which differ from each other in coordination sequences and / or dimensionality. - Graphical abstract: Crystal structures of two new uranium(VI) coordination polymers with succinate linkers, namely K{sub 2}[(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}] (1) and [Mg(H{sub 2}O){sub 6}][(UO{sub 2}){sub 2}(C{sub 4}H{sub 4}O{sub 4}){sub 3}]·2H{sub 2}O (2), were determined by single-crystal XRD. Crystals of studied compounds are based on 2D or 1D structural units with the same composition and crystallochemical formula. Topological isomerism in A{sub 2}Q{sup 02}{sub 3} crystallochemical group and conformations of succinate anions in uranyl complexes are under discussion. - Highlights: • Two new uranium coordination polymers were synthesized. • Their structural units have the same composition and crystallochemical formula. • In spite the same composition and CCF dimensionality of units is different. • Structural features of uranyl CPs are affected by linker conformations.},
doi = {10.1016/J.JSSC.2017.02.010},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 248,
place = {United States},
year = {Sat Apr 15 00:00:00 EDT 2017},
month = {Sat Apr 15 00:00:00 EDT 2017}
}
  • Three (5:1:3, 1:1:1, and 2:1:6) ternary phases were discovered in the K{sub 2}MoO{sub 4}-AMoO{sub 4}-Zr(MoO{sub 4}){sub 2} system, where A is Mg or Mn. For A = Mg, the authors have synthesized 5:1:3 single crystals and determined their crystal structure from X-ray diffraction data (a CAD-4 automatic diffractometer, MoK{sub a} radiation, 1166 F(hkl), and R = 0.026). The compound crystallizes in the trigonal system with space group R3c, a = 10.576(1), c = 37.511(3) {Angstrom}, Z = 6, d{sub calc} = 3.576, and d{sub msd} = 3.54 g/cm{sup 3}. The structure is a three-dimensional composite framework of alternating Mo tetrahedramore » and (Mg, Zr) octahedra, which are linked via the common {Omicron} vertices. Potassium atoms of three kinds are located in large framework cavities. Their polyhedra (ten-vertex polyhedra and a cubeoctahedron) are linked together by common faces and edges to form infinite zigzag columns of a large section. When solving the structure, the authors refined the composition of the crystals and the distribution of Mg{sup 2+} and Zr{sup 4+} cations in the M(1) and M(2) positions resulting in the formula above.« less
  • Crystals of protopyroxene solid solution, Li/sub x/Sc/sub x/Mg/sub 2-x/Si/sub 2/O/sub 6/, 0.1 equal to or less than x equal to or less than 0.35, were grown, in solvents of the system Li/sub 2/O-V/sub 2/O/sub 5/-MoO/sub 3/, by cooling from 1350 to 650/sup 0/ at 1.5/sup 0/C per hour. The crystals are transparent, euhedral, and prismatic, elongate parallel to c and up to 15 x 4 x 3 mm in size, with well-developed (010), (110), and (121) faces. The cell edges used for structure analysis are: a = 9.251, b = 8.773, and c = 5.377A. Long-exposure x-ray precession photographs showedmore » no diffraction maxima inconsistent with space group Pbcn and no evidence of stack disorder. The crystal structure was refined from 1507 measured x-ray intensities, of which 826 were greater than 3sigma of the background intensity. Refinements of the structure in space groups P2/sub 1/cn, Pb2n, Pbc2/sub 1/, and P2/c yielded structures which did not differ significantly from that in space group Pbcn. The structure is ordered with all of the Sc/sup 3 +/ in M1 and all of the Li/sup +/ in M2.« less
  • The hydrothermal synthesis and the single-crystal structure of Mg{sub (1{minus}x)}Zn{sub x}(VOPO{sub 4}){sub 2}{center{underscore}dot}4H{sub 2}O (x {approximately} 0.28) are described. The structure of Mg{sub (1{minus}x)}Zn{sub x}(VOPO{sub 4}){sub 2}{center{underscore}dot}4H{sub 2}O consists of infinite (VOPO{sub 4}) layers, built from VO{sub 5} pyramids and PO{sub 4} tetrahedra, interconnected via Mg{sub (1{minus}x)}Zn{sub x}O{sub 2}(H{sub 2}O){sub 4} octahedra. It belongs in the triclinic space group P1 with parameters a = 6.251(4), b = 6.258(3), c = 8.065(2) {angstrom}, {alpha} = 112.85(2){degree}, {beta} = 112.86(2){degree}, and {gamma} = 89.93(3){degree}, V = 263.7(2) {angstrom}{sup 3}, R{sub 1} = 0.0257, and wR{sub 2} = 0.0638 for 1985 reflections (F{supmore » 2} {ge} 4{sigma}(F{sup 2})).« less
  • Abstract The novel phase K
  • The ammonia synthesis from nitrogen and hydrogen has been investigated over model single-crystal and polycrystalline foil rhenium catalysts at 20 atm reactant pressure and in the temperature range 720-900 K. The reaction rate is remarkably sensitive to the catalyst surface structure. A reactivity ratio of 1:94:920:2820 was found for the Re(0001), Re(1010), Re(1120), and Re(1121) crystal faces, respectively. The catalytic activity of rhenium for ammonia synthesis is higher the more open and rough the surface is. An apparent activation energy of 19.4 +/- 1.1 kcal/mol was observed, regardless, of the catalyst surface structure. Kinetic data, reactant pressure dependence, and deuteriummore » isotope effect indicate that, as in the case of iron, the rate-determining step is the dissociative chemisorption of the nitrogen molecule. Potassium metal adsorbed on the clean rhenium surface does not have any effect on the reaction rate. The coadsorption of potassium with oxygen does not suppress the reactivity of the catalyst and stabilization of potassium on the surface occurs. 27 references.« less