Reinvestigation of trilithium divanadium(III) tris­(orthophosphate), Li3V2(PO4)3, based on single-crystal X-ray data

Kee, Y.; Yun, H.

doi:10.1107/S1600536813001499

Volume 69
Part 2
Pages i11-i12
February 2013

Received 18 December 2012
Accepted 15 January 2013
Online 19 January 2013

Key indicators
Single-crystal X-ray study
T = 290 K
Mean (V-O) = 0.002 Å
R = 0.024
wR = 0.062
Data-to-parameter ratio = 11.2
Details

Reinvestigation of trilithium divanadium(III) tris(orthophosphate), Li₃V₂(PO₄)₃, based on single-crystal X-ray data

Yongho Kee ^a and Hoseop Yun ^a ^*

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

The structure of Li₃V₂(PO₄)₃ has been reinvestigated from single-crystal X-ray data. Although the results of the previous studies (all based on powder diffraction data) are comparable with our redetermination, all atoms were refined with anisotropic displacement parameters in the current study, and the resulting bond lengths are more accurate than those determined from powder diffraction data. The title compound adopts the Li₃Fe₂(PO₄)₃ structure type. The structure is composed of VO₆ octahedra and PO₄ tetrahedra by sharing O atoms to form the three-dimensional anionic framework ³[V₂(PO₄)₃]^3-. The positions of the Li⁺ ions in the empty channels can vary depending on the synthetic conditions. Bond-valence-sum calculations showed structures that are similar to the results of the present study seem to be more stable compared with others. The classical charge balance of the title compound can be represented as [Li⁺]₃[V³⁺]₂[P⁵⁺]₃[O^2-]₁₂.

Related literature

For the isotypic Li₃Fe₂(PO₄)₃ structure, see: Patoux et al. (2003). Structural studies of Li₃V₂(PO₄)₃ based on powder diffraction data have been reported previously by Yin et al. (2003); Patoux et al. (2003); Kuo et al. (2008); Yang et al. (2010); Fu et al. (2010). For ionic radii, see: Shannon (1976). For bond-valence calculations, see: Adams (2001). For the Inorganic Crystal Structure Database, see: ICSD (2012).

Experimental

Crystal data

Li₃V₂(PO₄)₃
M_r = 407.61
Monoclinic, P 2₁ /c
a = 8.6201 (4) Å
b = 8.6013 (4) Å
c = 14.7465 (7) Å
= 125.204 (3)°
V = 893.39 (7) Å³
Z = 4
Mo K radiation
= 2.70 mm^-1
T = 290 K
0.08 × 0.04 × 0.04 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995) T_min = 0.741, T_max = 1.000
8328 measured reflections
2031 independent reflections
1772 reflections with I > 2(I)
R_int = 0.031

Refinement

R[F² > 2(F²)] = 0.024
wR(F²) = 0.062
S = 1.08
2031 reflections
181 parameters
_max = 0.58 e Å^-3
_min = -0.49 e Å^-3

Table 1
Selected bond lengths (Å)

Li1-O4	1.930 (6)
Li1-O5	1.940 (6)
Li1-O3ⁱ	2.094 (6)
Li1-O10ⁱⁱ	2.215 (6)
Li2-O3	1.968 (6)
Li2-O1	1.974 (6)
Li2-O7	2.004 (6)
Li2-O9	2.153 (7)
Li3-O6	1.944 (5)
Li3-O10	1.946 (5)
Li3-O11	1.994 (5)
Li3-O9	2.014 (6)
V1-O2	1.9040 (19)
V1-O8	1.954 (2)
V1-O1ⁱ	2.0163 (19)
V1-O7	2.0168 (18)
V1-O5	2.0450 (18)
V1-O3ⁱ	2.1172 (18)
V2-O12ⁱⁱⁱ	1.9099 (19)
V2-O6	1.9810 (18)
V2-O4	2.0012 (18)
V2-O11	2.0316 (18)
V2-O10ⁱⁱ	2.0343 (19)
V2-O9ⁱⁱ	2.0618 (18)
P1-O2^iv	1.5199 (19)
P1-O4^v	1.5297 (19)
P1-O1	1.5310 (19)
P1-O6	1.5400 (18)
P2-O8^vi	1.492 (2)
P2-O9	1.5419 (19)
P2-O7	1.5458 (18)
P2-O10ⁱⁱ	1.5497 (19)
P3-O12	1.5101 (19)
P3-O11	1.5343 (19)
P3-O5^vii	1.5454 (19)
P3-O3ⁱⁱ	1.5506 (18)
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) -x+1, -y+1, -z; (iv) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (v) -x, -y+1, -z; (vi) -x+1, -y+1, -z+1; (vii) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO; data reduction: RAPID-AUTO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 1999); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WM2716 ).

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

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inorganic compounds