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Volume 69 
Part 10 
Page i72  
October 2013  

Received 17 September 2013
Accepted 24 September 2013
Online 28 September 2013

Key indicators
Single-crystal X-ray study
T = 290 K
Mean [sigma](P-O) = 0.002 Å
Disorder in solvent or counterion
R = 0.026
wR = 0.068
Data-to-parameter ratio = 10.7
Details
Open access

The monoclinic form of trilithium dichromium(III) tris(orthophosphate)

aDepartment of Energy Systems Research and Department of Chemistry, Ajou University, Suwon 443-749, Republic of Korea
Correspondence e-mail: hsyun@ajou.ac.kr

The monoclinic form of trilithium dichromium(III) tris(orthophosphate), Li3Cr2(PO4)3, was prepared by the reactive halide flux method. The structure of the title compound is composed of a three-dimensional anionic framework with composition [infinity] 3[Cr2(PO4)3]3- and Li+ ions situated in the empty channels. The rigid framework built up from CrO6 octahedra and PO4 tetrahedra is the same as that found in other monoclinic Li3M2(PO4)3 (M = Fe, Sc, V) phases. The three Li+ cations of Li3Cr2(PO4)3 are unequally disordered over six crystallographically different sites. The classical charge balance of the title compound can be represented as [Li+]3[Cr3+]2[P5+]3[O2-]12. Solid-state UV/Vis spectra indicate that the crystal filed splitting ([Delta]0) of the Cr3+ ion is around 2.22 eV.

Related literature

For the structures of Li3M2(PO4)3 (M = Fe, Sc, Cr, V), see: d'Yvoire et al. (1983[d'Yvoire, F., Pintard-Scrépel, M., Bretey, E. & de la Rochère, M. (1983). Solid State Ionics, 9-10, 851-858.]); Verin et al. (1985[Verin, I. A., Genkina, E. A., Maksimov, B. A., Muradyan, L. A. & Sirota, M. I. (1985). Kristallografiya, 30, 677-681.]); Maksimov et al. (1986[Maksimov, B. A., Muradyan, L. A., Genkina, E. A. & Simonov, V. I. (1986). Dokl. Akad. Nauk SSSR, 288, 634-638.]). The structures of the orthorhombic form of Li3Cr2(PO4)3 have been investigated by Genkina et al. (1991[Genkina, E. A., Maksimov, B. A., Sigarev, S. E. & Verin, I. A. (1991). Kristallografiya, 31, 637-641.]). Structural studies of Li3V2(PO4)3 based on single-crystal data have been reported previously by Kee & Yun (2013[Kee, Y. & Yun, H. (2013). Acta Cryst. E69, i11-i12.]). The general structural features of the monoclinic phases have been discussed by Patoux et al. (2003[Patoux, S., Wurm, C., Morcrette, M., Rousse, G. & Masquelier, C. (2003). J. Power Sources, 119, 278-284.]); Fu et al. (2010[Fu, P., Zhao, Y., Dong, Y. & Hou, X. (2010). J. Phys. Chem. Solids, 71, 394-399.]); Yang et al. (2010[Yang, G., Ji, H. M., Liu, H., Qian, B. & Jiang, X. (2010). Electrochim. Acta, 55, 3669-3680.]). For ionic radii, see: Shannon (1976[Shannon, R. D. (1976). Acta Cryst. A32, 751-767.]).

Experimental

Crystal data
  • Li3Cr2(PO4)3

  • Mr = 409.73

  • Monoclinic, P 21 /c

  • a = 8.4625 (4) Å

  • b = 8.5560 (3) Å

  • c = 14.5344 (5) Å

  • [beta] = 125.186 (2)°

  • V = 860.08 (6) Å3

  • Z = 4

  • Mo K[alpha] radiation

  • [mu] = 3.16 mm-1

  • T = 290 K

  • 0.36 × 0.12 × 0.10 mm

Data collection
  • Rigaku R-AXIS RAPID S diffractometer

  • Absorption correction: multi-scan (ABSCOR; Higashi, 1995[Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.]) Tmin = 0.688, Tmax = 1.000

  • 8163 measured reflections

  • 1962 independent reflections

  • 1887 reflections with I > 2[sigma](I)

  • Rint = 0.021

Refinement
  • R[F2 > 2[sigma](F2)] = 0.026

  • wR(F2) = 0.068

  • S = 1.14

  • 1962 reflections

  • 184 parameters

  • 1 restraint

  • [Delta][rho]max = 0.71 e Å-3

  • [Delta][rho]min = -0.71 e Å-3

Data collection: RAPID-AUTO (Rigaku, 2006[Rigaku (2006). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.]); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: DIAMOND (Brandenburg, 1999[Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 2012[Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.]) and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).


Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2772 ).


Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea funded by the Ministry of Education, Science and Technology (grant No. 2011-0011309).

References

Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849-854.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Fu, P., Zhao, Y., Dong, Y. & Hou, X. (2010). J. Phys. Chem. Solids, 71, 394-399.  [Web of Science] [CrossRef] [ChemPort]
Genkina, E. A., Maksimov, B. A., Sigarev, S. E. & Verin, I. A. (1991). Kristallografiya, 31, 637-641.
Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan.
Kee, Y. & Yun, H. (2013). Acta Cryst. E69, i11-i12.  [CrossRef] [ChemPort] [IUCr Journals]
Maksimov, B. A., Muradyan, L. A., Genkina, E. A. & Simonov, V. I. (1986). Dokl. Akad. Nauk SSSR, 288, 634-638.  [ChemPort]
Patoux, S., Wurm, C., Morcrette, M., Rousse, G. & Masquelier, C. (2003). J. Power Sources, 119, 278-284.  [Web of Science] [CrossRef]
Rigaku (2006). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan.
Shannon, R. D. (1976). Acta Cryst. A32, 751-767.  [CrossRef] [IUCr Journals]
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.  [CrossRef] [ChemPort] [IUCr Journals]
Verin, I. A., Genkina, E. A., Maksimov, B. A., Muradyan, L. A. & Sirota, M. I. (1985). Kristallografiya, 30, 677-681.  [ChemPort]
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.  [Web of Science] [CrossRef] [ChemPort] [IUCr Journals]
Yang, G., Ji, H. M., Liu, H., Qian, B. & Jiang, X. (2010). Electrochim. Acta, 55, 3669-3680.  [Web of Science] [CrossRef] [ChemPort]
d'Yvoire, F., Pintard-Scrépel, M., Bretey, E. & de la Rochère, M. (1983). Solid State Ionics, 9-10, 851-858.  [CrossRef] [ChemPort] [Web of Science]


Acta Cryst (2013). E69, i72  [ doi:10.1107/S1600536813026433 ]

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