Searching for “LiCr{sup II}PO{sub 4}”
Abstract
The two new phosphates LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} and Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} are discovered as equilibrium phases (ϑ=800 °C) in the quarternary system Li/Cr/P/O. Their crystal structures have been determined from single-crystal X-ray diffraction data (LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}: violet-blue, Pnma (no. 62), Z=4, a=6.175(1) Å, b=14.316(3) Å, c=10.277(2) Å, 100 parameters, R{sub 1}=0.028, wR{sub 2}=0.08, 2060 unique reflections with F{sub o}>4σ(F{sub o}); Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}: greyish-green, P1{sup ¯} (no. 2), Z=1, a=4.9379(7) Å, b=7.917(2) Å, c=8.426(2) Å, α=109.98(2)°, β=90.71(1)°, γ=104.91(1)°, 131 parameters, R{sub 1}=0.022, wR{sub 2}=0.067, 1594 unique reflections with F{sub o}>4σ(F{sub o})). Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} adopts an hitherto unknown structure type. The crystal structure of LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} is isotypic to that of NaCd{sup II}{sub 4}(PO{sub 4}){sub 3} and related to that of the mineral silicocarnotite Ca{sub 5}(PO{sub 4}){sub 2}(SiO{sub 4}). Significant disorder between Li{sup +} and Cr{sup 2+} is observed for both crystal structures. The oxidation states assigned to chromium in these two phosphates are in agreement with UV/vis/NIR absorption spectra and magnetic susceptibility data recorded for both compounds. Instead of “LiCr{sup II}PO{sub 4}” mixtures of LiCr{sup II}{sub 4}(PO{sub 4}){sub 3},more »
- Authors:
-
- Institut für Anorganische Chemie, Universität Bonn, Gerhard-Domagk-Straße 1, D-53121 Bonn (Germany)
- Max-Planck-Institut für Festkörperforschung, Heisenbergstraße 1, D-70569 Stuttgart (Germany)
- Publication Date:
- OSTI Identifier:
- 22443421
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Solid State Chemistry
- Additional Journal Information:
- Journal Volume: 218; Other Information: Copyright (c) 2014 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; ABSORPTION SPECTRA; CATHODES; CATIONS; CHROMATES; CHROMIUM IONS; LITHIUM IONS; MAGNETIC SUSCEPTIBILITY; MIXTURES; MONOCRYSTALS; ORTHORHOMBIC LATTICES; PARAMAGNETISM; PHOSPHATES; REFLECTION; SILICATES; SILICON OXIDES; SIMULATION; SOLIDS; SPECTROSCOPY; SYNTHESIS; X-RAY DIFFRACTION
Citation Formats
Mosymow, E., Glaum, R., E-mail: rglaum@uni-bonn.de, and Kremer, R. K. Searching for “LiCr{sup II}PO{sub 4}”. United States: N. p., 2014.
Web. doi:10.1016/J.JSSC.2014.06.020.
Mosymow, E., Glaum, R., E-mail: rglaum@uni-bonn.de, & Kremer, R. K. Searching for “LiCr{sup II}PO{sub 4}”. United States. https://doi.org/10.1016/J.JSSC.2014.06.020
Mosymow, E., Glaum, R., E-mail: rglaum@uni-bonn.de, and Kremer, R. K. 2014.
"Searching for “LiCr{sup II}PO{sub 4}”". United States. https://doi.org/10.1016/J.JSSC.2014.06.020.
@article{osti_22443421,
title = {Searching for “LiCr{sup II}PO{sub 4}”},
author = {Mosymow, E. and Glaum, R., E-mail: rglaum@uni-bonn.de and Kremer, R. K.},
abstractNote = {The two new phosphates LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} and Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} are discovered as equilibrium phases (ϑ=800 °C) in the quarternary system Li/Cr/P/O. Their crystal structures have been determined from single-crystal X-ray diffraction data (LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}: violet-blue, Pnma (no. 62), Z=4, a=6.175(1) Å, b=14.316(3) Å, c=10.277(2) Å, 100 parameters, R{sub 1}=0.028, wR{sub 2}=0.08, 2060 unique reflections with F{sub o}>4σ(F{sub o}); Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}: greyish-green, P1{sup ¯} (no. 2), Z=1, a=4.9379(7) Å, b=7.917(2) Å, c=8.426(2) Å, α=109.98(2)°, β=90.71(1)°, γ=104.91(1)°, 131 parameters, R{sub 1}=0.022, wR{sub 2}=0.067, 1594 unique reflections with F{sub o}>4σ(F{sub o})). Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} adopts an hitherto unknown structure type. The crystal structure of LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} is isotypic to that of NaCd{sup II}{sub 4}(PO{sub 4}){sub 3} and related to that of the mineral silicocarnotite Ca{sub 5}(PO{sub 4}){sub 2}(SiO{sub 4}). Significant disorder between Li{sup +} and Cr{sup 2+} is observed for both crystal structures. The oxidation states assigned to chromium in these two phosphates are in agreement with UV/vis/NIR absorption spectra and magnetic susceptibility data recorded for both compounds. Instead of “LiCr{sup II}PO{sub 4}” mixtures of LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}, Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}, Cr{sub 2}O{sub 3}, and CrP are observed at equilibrium. Instead of “Li{sub 2}Cr{sup II}P{sub 2}O{sub 7}” four-phase mixtures consisting of Li{sub 9}Cr{sup III}{sub 3}(P{sub 2}O{sub 7}){sub 3}(PO{sub 4}){sub 2}, Li{sub 3}Cr{sup III}{sub 2}(PO{sub 4}){sub 3}, LiCrP{sub 2}O{sub 7}, and CrP were obtained. - Graphical abstract: Investigations on the equilibrium relations in the system Li/Cr/P/O revealed the two hitherto unknown phosphates Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} and LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}. They form instead of “LiCr{sup II}PO{sub 4}”. The crystal structures, magnetic behavior and optical spectra of these phosphates are reported. - Highlights: • The two new phosphates Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} and LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} have been characterized. • Optical spectra and paramagnetism of the these phosphates are explained by AOM. • Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4}, LiCr{sup II}{sub 4}(PO{sub 4}){sub 3}, Cr{sub 2}O{sub 3}, and CrP occur instead of “LiCr{sup II}PO{sub 4}”. • LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} is structurally closely related to Silicocarnotite Ca{sub 5}(PO{sub 4}){sub 2}(SiO{sub 4}). • Li{sub 5}Cr{sup II}{sub 2}Cr{sup III}(PO{sub 4}){sub 4} and LiCr{sup II}{sub 4}(PO{sub 4}){sub 3} exhibit significant cation disorder Li{sup +}/Cr{sup 2+}.},
doi = {10.1016/J.JSSC.2014.06.020},
url = {https://www.osti.gov/biblio/22443421},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 218,
place = {United States},
year = {Wed Oct 15 00:00:00 EDT 2014},
month = {Wed Oct 15 00:00:00 EDT 2014}
}