Reinvestigation of trilithium divanadium(III) tris-(orthophosphate), Li(3)V(2)(PO(4))(3), based on single-crystal X-ray data.

The structure of Li(3)V(2)(PO(4))(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 Li(3)Fe(2)(PO(4))(3) structure type. The structure is composed of VO(6) octa-hedra and PO(4) tetra-hedra by sharing O atoms to form the three-dimensional anionic framework (∞) (3)[V(2)(PO(4))(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)[V(3+)](2)[P(5+)](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 = 407.61

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.024

wR(F 2) = 0.062

S = 1.08

2031 reflections

181 parameters

Δρmax = 0.58 e Å−3

Δρmin = −0.49 e Å−3

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 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536813001499/wm2716sup1.cif

Click here for additional data file.

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Li3V2(PO4)3	F(000) = 784
Mr = 407.61	Dx = 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

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

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(Fo2) + (0.0223P)2 + 1.8904P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
2031 reflections	Δρmax = 0.58 e Å−3
181 parameters	Δρmin = −0.49 e Å−3

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.

	x	y	z	Uiso*/Ueq
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)

	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)

Li1—O4	1.930 (6)	V2—O12iv	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—O2v	1.5199 (19)
Li2—O9	2.153 (7)	P1—O4vi	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—O8vii	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—O5viii	1.5454 (19)
V1—O5	2.0450 (18)	P3—O3ii	1.5506 (18)
V1—O3i	2.1172 (18)
O4—Li1—O5	131.6 (3)	O2v—P1—O1	114.61 (12)
O4—Li1—O3i	135.8 (3)	O4vi—P1—O1	112.35 (11)
O5—Li1—O3i	80.6 (2)	O2v—P1—O6	107.88 (11)
O4—Li1—O10ii	80.9 (2)	O4vi—P1—O6	110.77 (10)
O5—Li1—O10ii	95.2 (2)	O1—P1—O6	106.40 (11)
O3i—Li1—O10ii	132.1 (3)	O8vii—P2—O9	113.49 (11)
O4—Li1—O7	134.8 (3)	O8vii—P2—O7	114.38 (12)
O5—Li1—O7	78.88 (19)	O9—P2—O7	104.68 (10)
O3i—Li1—O7	71.26 (18)	O8vii—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—O5viii	110.34 (11)
O3—Li2—O9	128.1 (3)	O11—P3—O5viii	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)	O5viii—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)	P1ix—O2—V1	153.03 (13)
O1—Li2—O5iii	69.03 (19)	P3viii—O3—Li2	109.4 (2)
O7—Li2—O5iii	97.6 (3)	P3viii—O3—Li1iii	128.10 (19)
O9—Li2—O5iii	165.3 (3)	Li2—O3—Li1iii	103.1 (3)
P2—Li2—O5iii	130.8 (3)	P3viii—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)	P1vi—O4—Li1	108.2 (2)
O6—Li3—O9	100.9 (2)	P1vi—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)	P2vii—O8—V1	168.23 (14)
O12iv—V2—O6	98.48 (8)	P2—O9—Li3	118.30 (18)
O12iv—V2—O4	93.92 (8)	P2—O9—V2viii	136.43 (11)
O6—V2—O4	88.86 (8)	Li3—O9—V2viii	96.15 (16)
O12iv—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)	V2viii—O9—Li2	109.31 (19)
O12iv—V2—O10ii	171.87 (8)	P2viii—O10—Li3	113.29 (19)
O6—V2—O10ii	89.34 (8)	P2viii—O10—V2viii	141.17 (12)
O4—V2—O10ii	83.96 (8)	Li3—O10—V2viii	99.23 (17)
O11—V2—O10ii	88.56 (8)	P2viii—O10—Li1viii	103.99 (17)
O12iv—V2—O9ii	92.40 (8)	Li3—O10—Li1viii	97.5 (2)
O6—V2—O9ii	167.76 (8)	V2viii—O10—Li1viii	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)
O2v—P1—O4vi	104.81 (11)	P3—O12—V2iv	166.44 (13)

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—O2iv	1.5199 (19)
P1—O4v	1.5297 (19)
P1—O1	1.5310 (19)
P1—O6	1.5400 (18)
P2—O8vi	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—O5vii	1.5454 (19)
P3—O3ii	1.5506 (18)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .