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

inorganic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Pages i11-i12

doi:10.1107/S1600536813001499

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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

(Received 18 December 2012; accepted 15 January 2013; online 19 January 2013)

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[O²⁻]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
β = 125.204 (3)°
V = 893.39 (7) Å³
Z = 4
Mo Kα radiation
μ = 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 > 2σ(I)
R_int = 0.031

Refinement

R[F² > 2σ(F²)] = 0.024
wR(F²) = 0.062
S = 1.08
2031 reflections
181 parameters
Δρ_max = 0.58 e Å⁻³
Δρ_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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536813001499/wm2716sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001499/wm2716Isup2.hkl

checkCIF report

Comment top

Trilithium divanadium(III) tris(orthophosphate), Li₃V₂(PO₄)₃, has been investigated as a cathode material of secondary batteries (Yin et al., 2003) and its structure has been reported based on powder diffraction data (Yin et al., 2003; Patoux et al., 2003; Kuo et al., 2008; Yang et al., 2010; Fu et al., 2010). In an attempt to prepare new mixed-metal phosphates using LiCl as a flux, we were able to isolate crystals of Li₃V₂(PO₄)₃, and report here the results of the structure analysis based on single-crystal X-ray diffraction data.

The title compound adopts the Li₃Fe₂(PO₄)₃ structure type. The general structural features of this compound are the same as reported previously (Patoux et al., 2003; Fu et al., 2010). However, as would be expected, the bond lengths found here from single-crystal diffraction data are more accurate than those reported previously from powder diffraction data. For example, the V—O distances (Table 1) reported by Kuo et al. (2008) range from 1.846 (3) to 2.258 (4) Å compared with 1.904 (2)–2.117 (2) Å here. Figure 1 shows the local coordination environment of the V and P atoms. In the structure, VO₆ octahedra are joined to PO₄ tetrahedra forming a [V₂(PO₄)₃] unit. These units share a terminal oxygen atom to construct the anionic three-dimensional framework, _∞³[V₂(PO₄)₃]^3- (Fig. 2). The V—O distances are in good agreement with those calculated from their ionic radii (1.99 Å, Shannon, 1976), assuming a valence of +III for V.

The Li⁺ ions in the empty channels are surrounded by four O atoms in distorted tetrahedral coordination sites. There are three crystallographically independent Li sites for this phase. It has been reported that the positions of the Li atoms can vary depending on the synthetic conditions while those of the V, P, and O atoms comprising the rigid framework remain intact (Yang et al., 2010). The Li positions found from the present single-crystal study are consistent with those reported by Patoux et al.(2003) and of a sample treated with microwave radiation at 1123 K for 3 min by Yang et al. (2010). According to bond valence sum calculations (Adams, 2001) for the various structure determinations, our study gives the lowest global instability index, Gii = 0.027. The Gii values of structures with Li positions similar to ours are likewise relatively low (i.e. 0.079; Yang et al., 2010), while those with Li positions considerably different as those from the present structures are much higher (i.e. 0.175; Yin et al., 2003).

The classical charge balance of the title compound can be represented as [Li⁺]₃[V³⁺]₂[P⁵⁺]₃[O^2-]₁₂.

Related literature top

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 top

The title compound, Li₃V₂(PO₄)₃, was prepared by the reaction of the elements with the use of the reactive halide-flux technique. A combination of the pure elements, Nb powder (Alfa Aesar 99.8%), V powder (STREM CHEMICALS 99.5%) and P powder (CERAC 99.5%) were mixed in a fused silica tube in a molar ratio of Nb:V:P = 1:1:3 and then LiCl (Sigma-Aldrich 99%) was added. The mass ratio of the reactants and the halide was 1:5. The tube was evacuated to 0.133 Pa, sealed, and heated gradually (150 K/h) to 1123 K, where it was kept for 12 h. The tube was cooled to room temperature at a rate of 3 K/h. The excess halide was removed with water and colourless block-shaped crystals were obtained. The crystals are stable in air and water. A qualitative X-ray fluorescence analysis of selected crystal indicated the presence of V, P, and O. The composition of the compound was determined by single-crystal X-ray diffraction.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 2006); cell refinement: RAPID-AUTO (Rigaku, 2006); data reduction: RAPID-AUTO (Rigaku, 2006); 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).

Figures top

	Fig. 1. A view showing the local coordination environments of the V and P atoms with the atom labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. Symmetry codes are as given in Table 1.
	Fig. 2. View of Li₃V₂(PO₄)₃ down the b axis. VO₆ octahedra are shown in blue and PO₄ tetrahedra are shown in pink.

Trilithium divanadium(III) tris(orthophosphate) top

Crystal data top

Li₃V₂(PO₄)₃	F(000) = 784
M_r = 407.61	D_x = 3.03 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.6201 (4) Å	Cell parameters from 5732 reflections
b = 8.6013 (4) Å	θ = 3.4–27.6°
c = 14.7465 (7) Å	µ = 2.70 mm⁻¹
β = 125.204 (3)°	T = 290 K
V = 893.39 (7) Å³	Block, colourless
Z = 4	0.08 × 0.04 × 0.04 mm

Data collection top

Rigaku R-AXIS RAPID diffractometer	1772 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ω scans	θ_max = 27.5°, θ_min = 3.4°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −11→10
T_min = 0.741, T_max = 1.000	k = −10→11
8328 measured reflections	l = −19→19
2031 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F² > 2σ(F²)] = 0.024	Secondary atom site location: difference Fourier map
wR(F²) = 0.062	w = 1/[σ²(F_o²) + (0.0223P)² + 1.8904P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
2031 reflections	Δρ_max = 0.58 e Å⁻³
181 parameters	Δρ_min = −0.49 e Å⁻³

Crystal data top

Li₃V₂(PO₄)₃	V = 893.39 (7) Å³
M_r = 407.61	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.6201 (4) Å	µ = 2.70 mm⁻¹
b = 8.6013 (4) Å	T = 290 K
c = 14.7465 (7) Å	0.08 × 0.04 × 0.04 mm
β = 125.204 (3)°

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.024	181 parameters
wR(F²) = 0.062	0 restraints
S = 1.08	Δρ_max = 0.58 e Å⁻³
2031 reflections	Δρ_min = −0.49 e Å⁻³

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Li1	0.1133 (8)	0.5883 (7)	0.1934 (4)	0.0266 (12)
Li2	0.1891 (9)	0.1919 (7)	0.2599 (5)	0.0356 (15)
Li3	0.4730 (7)	0.2213 (6)	0.1767 (4)	0.0186 (10)
V1	0.13814 (6)	0.52846 (5)	0.38977 (4)	0.00672 (11)
V2	0.36217 (6)	0.53898 (5)	0.11037 (3)	0.00643 (11)
P1	0.04417 (9)	0.25109 (7)	0.00782 (5)	0.00655 (14)
P2	0.45782 (9)	0.39759 (8)	0.35181 (5)	0.00672 (14)
P3	0.75192 (9)	0.38467 (7)	0.14738 (5)	0.00638 (14)
O1	0.0267 (3)	0.1788 (2)	0.09643 (16)	0.0126 (4)
O2	0.0361 (3)	0.3649 (2)	0.42742 (16)	0.0150 (4)
O3	0.0850 (2)	0.0021 (2)	0.28038 (15)	0.0102 (4)
O4	0.1152 (3)	0.6330 (2)	0.06577 (16)	0.0111 (4)
O5	0.1785 (3)	0.7151 (2)	0.31962 (15)	0.0109 (4)
O6	0.2392 (2)	0.3319 (2)	0.07040 (16)	0.0112 (4)
O7	0.2789 (3)	0.3861 (2)	0.35185 (16)	0.0125 (4)
O8	0.3675 (3)	0.5514 (2)	0.54043 (16)	0.0171 (4)
O9	0.4764 (3)	0.2357 (2)	0.31413 (15)	0.0099 (4)
O10	0.5906 (3)	0.0200 (2)	0.23807 (15)	0.0116 (4)
O11	0.5994 (3)	0.4098 (2)	0.16881 (15)	0.0110 (4)
O12	0.6748 (3)	0.4125 (2)	0.02723 (15)	0.0128 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Li1	0.030 (3)	0.038 (3)	0.017 (3)	−0.008 (3)	0.017 (2)	−0.005 (2)
Li2	0.042 (3)	0.030 (3)	0.022 (3)	−0.020 (3)	0.010 (3)	−0.001 (2)
Li3	0.018 (2)	0.016 (2)	0.021 (3)	0.003 (2)	0.011 (2)	0.004 (2)
V1	0.0067 (2)	0.0061 (2)	0.0080 (2)	−0.00005 (16)	0.00464 (17)	0.00055 (15)
V2	0.0069 (2)	0.0060 (2)	0.0073 (2)	−0.00006 (15)	0.00458 (17)	0.00017 (15)
P1	0.0062 (3)	0.0055 (3)	0.0086 (3)	0.0001 (2)	0.0046 (2)	0.0000 (2)
P2	0.0066 (3)	0.0062 (3)	0.0073 (3)	0.0005 (2)	0.0040 (2)	−0.0001 (2)
P3	0.0063 (3)	0.0058 (3)	0.0078 (3)	−0.0002 (2)	0.0046 (2)	−0.0005 (2)
O1	0.0118 (9)	0.0150 (9)	0.0122 (9)	−0.0020 (7)	0.0076 (8)	0.0018 (8)
O2	0.0147 (9)	0.0146 (10)	0.0143 (10)	−0.0023 (8)	0.0076 (8)	0.0053 (8)
O3	0.0106 (8)	0.0081 (8)	0.0093 (9)	0.0027 (7)	0.0042 (7)	0.0009 (7)
O4	0.0104 (8)	0.0107 (9)	0.0133 (9)	0.0034 (7)	0.0074 (8)	0.0015 (7)
O5	0.0163 (9)	0.0075 (9)	0.0119 (9)	−0.0022 (7)	0.0099 (8)	−0.0003 (7)
O6	0.0081 (8)	0.0088 (9)	0.0140 (10)	−0.0015 (7)	0.0048 (8)	−0.0002 (7)
O7	0.0128 (9)	0.0105 (9)	0.0191 (10)	−0.0010 (7)	0.0120 (8)	−0.0031 (8)
O8	0.0094 (9)	0.0205 (10)	0.0131 (10)	−0.0009 (8)	0.0016 (8)	−0.0051 (8)
O9	0.0133 (9)	0.0062 (8)	0.0106 (9)	0.0022 (7)	0.0071 (7)	0.0002 (7)
O10	0.0173 (9)	0.0088 (9)	0.0110 (9)	−0.0016 (7)	0.0096 (8)	−0.0016 (7)
O11	0.0109 (8)	0.0124 (9)	0.0119 (9)	0.0027 (7)	0.0078 (8)	0.0020 (7)
O12	0.0136 (9)	0.0155 (9)	0.0100 (9)	0.0013 (8)	0.0072 (8)	0.0014 (7)

Geometric parameters (Å, º) top

Li1—O4	1.930 (6)	V2—O12^iv	1.9099 (19)
Li1—O5	1.940 (6)	V2—O6	1.9810 (18)
Li1—O3ⁱ	2.094 (6)	V2—O4	2.0012 (18)
Li1—O10ⁱⁱ	2.215 (6)	V2—O11	2.0316 (18)
Li1—O7	2.584 (6)	V2—O10ⁱⁱ	2.0343 (19)
Li2—O3	1.968 (6)	V2—O9ⁱⁱ	2.0618 (18)
Li2—O1	1.974 (6)	V2—Li3ⁱⁱ	3.032 (5)
Li2—O7	2.004 (6)	P1—O2^v	1.5199 (19)
Li2—O9	2.153 (7)	P1—O4^vi	1.5297 (19)
Li2—O5ⁱⁱⁱ	2.678 (7)	P1—O1	1.5310 (19)
Li3—O6	1.944 (5)	P1—O6	1.5400 (18)
Li3—O10	1.946 (5)	P2—O8^vii	1.492 (2)
Li3—O11	1.994 (5)	P2—O9	1.5419 (19)
Li3—O9	2.014 (6)	P2—O7	1.5458 (18)
V1—O2	1.9040 (19)	P2—O10ⁱⁱ	1.5497 (19)
V1—O8	1.954 (2)	P3—O12	1.5101 (19)
V1—O1ⁱ	2.0163 (19)	P3—O11	1.5343 (19)
V1—O7	2.0168 (18)	P3—O5^viii	1.5454 (19)
V1—O5	2.0450 (18)	P3—O3ⁱⁱ	1.5506 (18)
V1—O3ⁱ	2.1172 (18)

O4—Li1—O5	131.6 (3)	O2^v—P1—O1	114.61 (12)
O4—Li1—O3ⁱ	135.8 (3)	O4^vi—P1—O1	112.35 (11)
O5—Li1—O3ⁱ	80.6 (2)	O2^v—P1—O6	107.88 (11)
O4—Li1—O10ⁱⁱ	80.9 (2)	O4^vi—P1—O6	110.77 (10)
O5—Li1—O10ⁱⁱ	95.2 (2)	O1—P1—O6	106.40 (11)
O3ⁱ—Li1—O10ⁱⁱ	132.1 (3)	O8^vii—P2—O9	113.49 (11)
O4—Li1—O7	134.8 (3)	O8^vii—P2—O7	114.38 (12)
O5—Li1—O7	78.88 (19)	O9—P2—O7	104.68 (10)
O3ⁱ—Li1—O7	71.26 (18)	O8^vii—P2—O10ⁱⁱ	108.68 (12)
O10ⁱⁱ—Li1—O7	61.21 (16)	O9—P2—O10ⁱⁱ	109.75 (10)
O3—Li2—O1	94.3 (3)	O7—P2—O10ⁱⁱ	105.50 (11)
O3—Li2—O7	128.3 (4)	O12—P3—O11	111.68 (11)
O1—Li2—O7	126.8 (3)	O12—P3—O5^viii	110.34 (11)
O3—Li2—O9	128.1 (3)	O11—P3—O5^viii	106.92 (10)
O1—Li2—O9	108.5 (3)	O12—P3—O3ⁱⁱ	108.32 (11)
O7—Li2—O9	71.9 (2)	O11—P3—O3ⁱⁱ	108.17 (11)
O3—Li2—P2	146.7 (3)	O5^viii—P3—O3ⁱⁱ	111.42 (10)
O1—Li2—P2	117.9 (3)	P1—O1—Li2	132.1 (2)
O7—Li2—P2	36.57 (11)	P1—O1—V1ⁱⁱⁱ	140.21 (12)
O9—Li2—P2	36.48 (10)	Li2—O1—V1ⁱⁱⁱ	87.60 (18)
O3—Li2—O5ⁱⁱⁱ	66.43 (19)	P1^ix—O2—V1	153.03 (13)
O1—Li2—O5ⁱⁱⁱ	69.03 (19)	P3^viii—O3—Li2	109.4 (2)
O7—Li2—O5ⁱⁱⁱ	97.6 (3)	P3^viii—O3—Li1ⁱⁱⁱ	128.10 (19)
O9—Li2—O5ⁱⁱⁱ	165.3 (3)	Li2—O3—Li1ⁱⁱⁱ	103.1 (3)
P2—Li2—O5ⁱⁱⁱ	130.8 (3)	P3^viii—O3—V1ⁱⁱⁱ	136.75 (11)
O6—Li3—O10	146.1 (3)	Li2—O3—V1ⁱⁱⁱ	84.99 (19)
O6—Li3—O11	84.4 (2)	Li1ⁱⁱⁱ—O3—V1ⁱⁱⁱ	84.27 (16)
O10—Li3—O11	126.5 (3)	P1^vi—O4—Li1	108.2 (2)
O6—Li3—O9	100.9 (2)	P1^vi—O4—V2	147.84 (12)
O10—Li3—O9	83.4 (2)	Li1—O4—V2	101.8 (2)
O11—Li3—O9	108.5 (3)	P3ⁱⁱ—O5—Li1	132.7 (2)
O2—V1—O8	94.48 (9)	P3ⁱⁱ—O5—V1	136.88 (11)
O2—V1—O1ⁱ	88.48 (8)	Li1—O5—V1	90.28 (19)
O8—V1—O1ⁱ	97.50 (8)	P3ⁱⁱ—O5—Li2ⁱ	110.77 (16)
O2—V1—O7	94.88 (8)	Li1—O5—Li2ⁱ	85.6 (2)
O8—V1—O7	90.02 (8)	V1—O5—Li2ⁱ	70.11 (15)
O1ⁱ—V1—O7	171.50 (8)	P1—O6—Li3	121.90 (18)
O2—V1—O5	165.80 (8)	P1—O6—V2	142.76 (11)
O8—V1—O5	98.04 (8)	Li3—O6—V2	94.12 (17)
O1ⁱ—V1—O5	83.28 (8)	P2—O7—Li2	92.9 (2)
O7—V1—O5	91.80 (8)	P2—O7—V1	136.13 (12)
O2—V1—O3ⁱ	90.55 (8)	Li2—O7—V1	129.4 (2)
O8—V1—O3ⁱ	172.14 (8)	P2—O7—Li1	89.28 (15)
O1ⁱ—V1—O3ⁱ	88.65 (8)	Li2—O7—Li1	98.8 (2)
O7—V1—O3ⁱ	83.53 (8)	V1—O7—Li1	74.63 (14)
O5—V1—O3ⁱ	77.75 (7)	P2^vii—O8—V1	168.23 (14)
O12^iv—V2—O6	98.48 (8)	P2—O9—Li3	118.30 (18)
O12^iv—V2—O4	93.92 (8)	P2—O9—V2^viii	136.43 (11)
O6—V2—O4	88.86 (8)	Li3—O9—V2^viii	96.15 (16)
O12^iv—V2—O11	94.63 (8)	P2—O9—Li2	87.4 (2)
O6—V2—O11	82.50 (8)	Li3—O9—Li2	105.6 (2)
O4—V2—O11	168.64 (8)	V2^viii—O9—Li2	109.31 (19)
O12^iv—V2—O10ⁱⁱ	171.87 (8)	P2^viii—O10—Li3	113.29 (19)
O6—V2—O10ⁱⁱ	89.34 (8)	P2^viii—O10—V2^viii	141.17 (12)
O4—V2—O10ⁱⁱ	83.96 (8)	Li3—O10—V2^viii	99.23 (17)
O11—V2—O10ⁱⁱ	88.56 (8)	P2^viii—O10—Li1^viii	103.99 (17)
O12^iv—V2—O9ⁱⁱ	92.40 (8)	Li3—O10—Li1^viii	97.5 (2)
O6—V2—O9ⁱⁱ	167.76 (8)	V2^viii—O10—Li1^viii	91.67 (15)
O4—V2—O9ⁱⁱ	96.01 (8)	P3—O11—Li3	117.36 (18)
O11—V2—O9ⁱⁱ	91.09 (7)	P3—O11—V2	139.65 (12)
O10ⁱⁱ—V2—O9ⁱⁱ	80.05 (7)	Li3—O11—V2	91.10 (16)
O2^v—P1—O4^vi	104.81 (11)	P3—O12—V2^iv	166.44 (13)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x, y−1/2, −z+1/2; (iv) −x+1, −y+1, −z; (v) x, −y+1/2, z−1/2; (vi) −x, −y+1, −z; (vii) −x+1, −y+1, −z+1; (viii) −x+1, y−1/2, −z+1/2; (ix) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	Li₃V₂(PO₄)₃
M_r	407.61
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	290
a, b, c (Å)	8.6201 (4), 8.6013 (4), 14.7465 (7)
β (°)	125.204 (3)
V (Å³)	893.39 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.70
Crystal size (mm)	0.08 × 0.04 × 0.04

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.741, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	8328, 2031, 1772
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.024, 0.062, 1.08
No. of reflections	2031
No. of parameters	181
Δρ_max, Δρ_min (e Å⁻³)	0.58, −0.49

Computer programs: RAPID-AUTO (Rigaku, 2006), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg, 1999), WinGX (Farrugia, 2012).

Selected bond lengths (Å) top

Li1—O4	1.930 (6)	V2—O12ⁱⁱⁱ	1.9099 (19)
Li1—O5	1.940 (6)	V2—O6	1.9810 (18)
Li1—O3ⁱ	2.094 (6)	V2—O4	2.0012 (18)
Li1—O10ⁱⁱ	2.215 (6)	V2—O11	2.0316 (18)
Li2—O3	1.968 (6)	V2—O10ⁱⁱ	2.0343 (19)
Li2—O1	1.974 (6)	V2—O9ⁱⁱ	2.0618 (18)
Li2—O7	2.004 (6)	P1—O2^iv	1.5199 (19)
Li2—O9	2.153 (7)	P1—O4^v	1.5297 (19)
Li3—O6	1.944 (5)	P1—O1	1.5310 (19)
Li3—O10	1.946 (5)	P1—O6	1.5400 (18)
Li3—O11	1.994 (5)	P2—O8^vi	1.492 (2)
Li3—O9	2.014 (6)	P2—O9	1.5419 (19)
V1—O2	1.9040 (19)	P2—O7	1.5458 (18)
V1—O8	1.954 (2)	P2—O10ⁱⁱ	1.5497 (19)
V1—O1ⁱ	2.0163 (19)	P3—O12	1.5101 (19)
V1—O7	2.0168 (18)	P3—O11	1.5343 (19)
V1—O5	2.0450 (18)	P3—O5^vii	1.5454 (19)
V1—O3ⁱ	2.1172 (18)	P3—O3ⁱⁱ	1.5506 (18)

Symmetry codes: (i) −x, y+1/2, −z+1/2; (ii) −x+1, y+1/2, −z+1/2; (iii) −x+1, −y+1, −z; (iv) x, −y+1/2, z−1/2; (v) −x, −y+1, −z; (vi) −x+1, −y+1, −z+1; (vii) −x+1, y−1/2, −z+1/2.

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).

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