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Title: Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units

Abstract

Single crystals of Zn{sub 4}(OH){sub 2}[(UO{sub 2})(PO{sub 4}){sub 2}(OH){sub 2}(H{sub 2}O)] (UZnP), Cs[(UO{sub 2})(HPO{sub 4})NO{sub 3}] (UCsP), and In{sub 3}[(UO{sub 2}){sub 2}(PO{sub 4}){sub 4}OH(H{sub 2}O){sub 6}].2H{sub 2}O (UInP) were obtained from hydrothermal reactions and have been structurally and chemically characterized. UZnP crystallizes in space group Pbcn, a=8.8817(7), b=6.6109(5), c=19.569(1) A; UCsP crystallizes in P-1, a=7.015(2), b=7.441(1), c=9.393(2) A, {alpha}=72.974(2), {beta}=74.261(2), {gamma}=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) A {alpha}=101.289(1), {beta}=114.642(1), {gamma}=99.203(2). The U{sup 6+} cations are present as (UO{sub 2}){sup 2+} uranyl ions coordinated by five O atoms to give pentagonal bipyramids. The structural unit in UZnP is a finite cluster containing a uranyl pentagonal bipyramid that shares corners with two phosphate tetrahedra. The structural unit in UCsP is composed of uranyl pentagonal bipyramids with one chelating nitrate group that are linked into chains by three bridging hydrogen phosphate tetrahedra. In UInP, the structural unit contains pairs of edge-sharing uranyl pentagonal bipyramids with two chelating phosphate tetrahedra that are linked into chains through two bridging phosphate tetrahedra. Indium octahedra link these uranyl phosphate chains into a 3-dimensional framework. All three compounds exhibit unique structural units that deviate from the typical layered structures observed in uranyl phosphate solid-state chemistry.more » - Graphical abstract: Three new uranyl phosphates with unique structural units are reported. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Three new uranyl phosphates have been synthesized hydrothermally. Black-Right-Pointing-Pointer Single crystal analyses reveal unique structural units. Black-Right-Pointing-Pointer The dimensionality of these compounds deviate from typical U{sup 6+} layered structures.« less

Authors:
;  [1];  [1];  [2]
  1. Department of Civil and Environmental Engineering and Earth Sciences, University of Notre Dame, Notre Dame, IN 46556 (United States)
  2. (United States)
Publication Date:
OSTI Identifier:
22149972
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 196; Other Information: Copyright (c) 2012 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; 36 MATERIALS SCIENCE; CATIONS; CHAINS; CHELATING AGENTS; HYDROGEN PHOSPHATES; HYDROTHERMAL SYNTHESIS; INFRARED SPECTRA; MONOCRYSTALS; NITRATES; NITROGEN OXIDES; SOLIDS; SPACE GROUPS; URANIUM DIOXIDE; URANIUM IONS; URANYL PHOSPHATES; X-RAY DIFFRACTION

Citation Formats

Wylie, Ernest M., Dawes, Colleen M., Burns, Peter C., E-mail: pburns@nd.edu, and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556. Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units. United States: N. p., 2012. Web. doi:10.1016/J.JSSC.2012.07.020.
Wylie, Ernest M., Dawes, Colleen M., Burns, Peter C., E-mail: pburns@nd.edu, & Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556. Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units. United States. doi:10.1016/J.JSSC.2012.07.020.
Wylie, Ernest M., Dawes, Colleen M., Burns, Peter C., E-mail: pburns@nd.edu, and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556. Sat . "Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units". United States. doi:10.1016/J.JSSC.2012.07.020.
@article{osti_22149972,
title = {Synthesis, structure, and spectroscopic characterization of three uranyl phosphates with unique structural units},
author = {Wylie, Ernest M. and Dawes, Colleen M. and Burns, Peter C., E-mail: pburns@nd.edu and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556},
abstractNote = {Single crystals of Zn{sub 4}(OH){sub 2}[(UO{sub 2})(PO{sub 4}){sub 2}(OH){sub 2}(H{sub 2}O)] (UZnP), Cs[(UO{sub 2})(HPO{sub 4})NO{sub 3}] (UCsP), and In{sub 3}[(UO{sub 2}){sub 2}(PO{sub 4}){sub 4}OH(H{sub 2}O){sub 6}].2H{sub 2}O (UInP) were obtained from hydrothermal reactions and have been structurally and chemically characterized. UZnP crystallizes in space group Pbcn, a=8.8817(7), b=6.6109(5), c=19.569(1) A; UCsP crystallizes in P-1, a=7.015(2), b=7.441(1), c=9.393(2) A, {alpha}=72.974(2), {beta}=74.261(2), {gamma}=79.498(2); and UInP crystallizes in P-1, a=7.9856(5), b=9.159(1), c=9.2398(6) A {alpha}=101.289(1), {beta}=114.642(1), {gamma}=99.203(2). The U{sup 6+} cations are present as (UO{sub 2}){sup 2+} uranyl ions coordinated by five O atoms to give pentagonal bipyramids. The structural unit in UZnP is a finite cluster containing a uranyl pentagonal bipyramid that shares corners with two phosphate tetrahedra. The structural unit in UCsP is composed of uranyl pentagonal bipyramids with one chelating nitrate group that are linked into chains by three bridging hydrogen phosphate tetrahedra. In UInP, the structural unit contains pairs of edge-sharing uranyl pentagonal bipyramids with two chelating phosphate tetrahedra that are linked into chains through two bridging phosphate tetrahedra. Indium octahedra link these uranyl phosphate chains into a 3-dimensional framework. All three compounds exhibit unique structural units that deviate from the typical layered structures observed in uranyl phosphate solid-state chemistry. - Graphical abstract: Three new uranyl phosphates with unique structural units are reported. Black-Small-Square Highlights: Black-Right-Pointing-Pointer Three new uranyl phosphates have been synthesized hydrothermally. Black-Right-Pointing-Pointer Single crystal analyses reveal unique structural units. Black-Right-Pointing-Pointer The dimensionality of these compounds deviate from typical U{sup 6+} layered structures.},
doi = {10.1016/J.JSSC.2012.07.020},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 196,
place = {United States},
year = {Sat Dec 15 00:00:00 EST 2012},
month = {Sat Dec 15 00:00:00 EST 2012}
}
  • The reaction of triuranyl diphosphate tetrahydrate precursor (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} with a CsI flux at 750 °C yields a yellow single crystals of new compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. The crystal structure (monoclinic, space group C2/c, a=13.6261 (13) Å, b=8.1081(8) Å, c=12.3983(12) Å, β=114.61(12)°, V=1245.41(20) Å{sup 3} with Z=4) has been solved using direct methods and Fourier difference techniques. A full-matrix least-squares refinement on the basis of F{sup 2} yielded R1=0.028 and wR2=0.071 for 79 parameters and 1352 independent reflections with I≥2σ(I) collected on a BRUKER AXS diffractometer with MoKα radiation and a charge-coupledmore » device detector. The crystal structure is built by two independent uranium atoms in square bipyramidal coordination, connected by two opposite corners to form infinite chains {sup 1}{sub ∞}[UO{sub 5}] and by one phosphorus atom in a tetrahedral environment PO{sub 4}. The two last entities {sup 1}{sub ∞}[UO{sub 5}] and PO{sub 4} are linked by sharing corners to form a three-dimensional structure presenting different types of channels occupied by Cs{sup +} alkaline cations. Their mobility within the tunnels were studied between 280 and 800 °C and compared with other tunneled uranyl minerals. The infrared spectrum shows a good agreement with the values inferred from the single crystal structure analysis of uranyl phosphate compound. - Graphical abstract: Arrhenius plot of the electrical conductivity of tunneled compounds Cs{sub 3}U{sub 2}PO{sub 10} and CsU{sub 2}Nb{sub 2}O{sub 11.5}. Highlights: ► The reaction of (UO{sub 2}){sub 3}(PO{sub 4}){sub 2}(H{sub 2}O){sub 4} in excess of molten CsI leads to single-crystals of new tunneled compound Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2}. ► Ionic conductivity measurements and crystal structure analysis indicate a strong connection of the Cs{sup +} cations to the tunnels. ► A low symmetry in Cs{sub 3}(UO{sub 2}){sub 2}(PO{sub 4})O{sub 2} is the cause of IR activation and splitting of the bands in the IR spectrum.« less
  • Four new Li uranyl phosphates and arsenates have been prepared by high-temperature solid-state reactions: {alpha}-Li[(UO{sub 2})(PO{sub 4})] (1), {alpha}-Li[(UO{sub 2})(AsO{sub 4})] (2), {beta}-Li[(UO{sub 2})(AsO{sub 4})] (3) and Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] (4). The structures of the compounds have been solved by direct methods: 1-triclinic, P1-bar, a=5.0271(1) A, b=9.8799(2) A, c=10.8920(2) A, {alpha}=108.282(9){sup o}, {beta}=102.993(8){sup o}, {gamma}=104.13(1){sup o}, V=470.69(2) A{sup 3}, Z=4, R{sub 1}=0.0415 for 2786 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 2-triclinic, P1-bar, a=5.129(2) A, b=10.105(3) A, c=11.080(3) A, {alpha}=107.70(2){sup o}, {beta}=102.53(3){sup o}, {gamma}=104.74(3){sup o}, V=501.4(3) A{sup 3}, Z=4, R{sub 1}=0.055 for 1431 unique reflections with |F{submore » 0}|{>=}4{sigma}{sub F}; 3-triclinic, P1-bar, a=5.051(1) A, b=5.303(1) A, c=10.101(1) A, {alpha}=90.31(1){sup o}, {beta}=97.49(1){sup o}, {gamma}=105.08(1){sup o}, V=258.80(8) A{sup 3}, Z=2, R{sub 1}=0.0339 for 2055 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}; 4-triclinic, P1-bar, a=5.312(1) A, b=6.696(1) A, c=12.542(1) A, {alpha}=94.532(9){sup o}, {beta}=99.059(8){sup o}, {gamma}=110.189(7){sup o}, V=409.17(10) A{sup 3}, Z=2, R{sub 1}=0.0565 for 1355 unique reflections with |F{sub 0}|{>=}4{sigma}{sub F}. The structures of all four compounds are based upon 3-D frameworks of U and T polyhedra (T=P, As). Phases 1 and 2 are isostructural and consist of U{sub 2}O{sub 12} dimers and UO{sub 6} square bipyramids linked by single TO{sub 4} tetrahedra. The structure of 3 consists of 3-D framework of corner-sharing UO{sub 6} bipyramids and AsO{sub 4} tetrahedra. In the structure of 4, the framework is composed of U{sub 2}O{sub 12} dimers, UO{sub 6} bipyramids and P{sub 2}O{sub 7} dimers. In all the compounds, Li{sup +} cations reside in framework cavities. The topologies of the 3-D frameworks can be described as derivatives of the PtS (cooperite) network. - Graphical abstract: Polyhedral and topological presentation of Li{sub 2}[(UO{sub 2}){sub 3}(P{sub 2}O{sub 7}){sub 2}] crystal structure.« less
  • In the present work, a chiral layered derivative of γ-zirconium phosphate (γ-ZrP) containing L-(+)-phosphoserine (γ-ZrP-PS*) covalently attached to inorganic layers has been prepared by means of topotactic exchange reaction. This organic–inorganic derivative is characterized by X-ray diffractometry, Solid {sup 13}C–NMR and FT-IR spectrophotometries and thermal analyses. A maximum level of topotactic replacement of 20% is achieved. Under both the acidic environment of the interlayer region of γ-ZrP and the acidic synthesis conditions, the hydrolysis of the ester bond of PS* is expected to take place to some extent. For this reason, it was impossible to exceed the recent percentage, whichmore » in turn reflects the relative moderate stability of the above mentioned bond under these conditions. In order to be more certain with regard to an expected further hydrolysis for this bond after separation, a sample of γ-ZrP-PS* was stored in a desiccator over a saturated solution of BaCl{sub 2} (90% relative humidity) for three months, and then the sample re-analyzed once again. Surprisingly, the results show that the sample still keeps almost the same level of exchange (i.e., 20%). Second, it is revealed that the sample almost gives the same spectroscopic and thermal behavior. This could be attributed to the less acidic character of the partially exchanged inorganic layers of the sample in comparison with that of the precursor γ-ZrP. Therefore, the PS* molecules persist and stay there into the interlayer gallery without further hydrolysis. - Graphical abstract: • Red: oxygen • White: zirconium • Cyan: carbon • Yellow: phosphorus • Blue: nitrogen. Highlights: • L-(+)-Phosphoserine (PS*) is exchanged with γ-ZrP by means of topotactic exchange. • The maximum exchange level is 20%. • γ-ZrP is functionalized with chiral amino acid group. • γ-ZrP-PS* has large chiral space for huge guest molecules to be intercalated.« less
  • The authors discuss the synthesis and structural characterization of (VO){sub 2}(PO{sub 4}){sub 2}H{sub 2}PO{sub 4}{sm_bullet}N{sub 2}C{sub 2}H{sub 10}. The structure consists of V{sup IV}O{sub 6}, V{sup v}O{sub 6}, PO{sub 4}, and H{sub 2}PO{sub 4} polyhedra, connected via V-O-P bonds. 19 refs., 4 figs.
  • Uranyl complexes of a bis(methylterephthalamide) ligand (LH{sub 4}) have been synthesized and characterized by X-ray crystallography. The structure is an unexpected [Me{sub 4}N]{sub 8}[L(UO{sub 2})]{sub 4} tetramer, formed via coordination of the two MeTAM units of L to two uranyl moieties. Addition of KOH to the tetramer gave the corresponding monomeric uranyl methoxide species [Me{sub 4}N]K{sub 2}[LUO{sub 2}(OMe)].