Lithium vanado(V)molybdate(VI), Li[VMoO6].

Brannerite-type Li[VMoO6] has been synthesized by a solid state reaction route. The V and Mo atoms statistically occupy the same site with mirror symmetry and are octa-hedrally surrounded by O atoms. The framework is two-dimensional and is built up from edge-sharing (V,Mo)O6 octa-hedra forming (VMoO6)∞ layers that run parallel to the (001) plane. Li(+) ions are situated in position with symmetry 2/m in the inter-layer space. The bond-valence analysis reveals that the Li(+) ionic conductivity is along the [010] and [110] directions, and shows that this material may have inter-esting conduction properties. This simulation proposes a model of the lithium conduction pathways.

Related literature

For background to lithium-ion batteries, see: Delmas et al. (1999 ▶); Cabana et al. (2003 ▶); Yin et al. (2003 ▶); Morgan et al. (2002 ▶); Gaubicher et al. (2000 ▶); Sato et al. (2000 ▶); Fu et al. (2010 ▶); Mikhailova et al. (2010 ▶). For details of structural relationships with other compounds, see: Andersson & Magnéli (1950 ▶); Darriet & Galy (1968 ▶); Karen et al. (2006 ▶); Knyazev et al. (2009 ▶); Mocala & Ziolkowski (1987 ▶); Mucha et al. (1999 ▶); Ruh & Wadsley (1966 ▶); Shklover et al. (1996 ▶). For details of the bond-valence method, see: Brown, (2002 ▶). For BVS pathway simulation, see: Mazza et al. (2002 ▶); Ben Smida et al. (2013 ▶); Mazza (2001 ▶); Ouerfelli et al. (2007a ▶,b ▶).

Experimental

Crystal data

LiMoVO6

M = 249.82

Monoclinic,

a = 9.3555 (9) Å

b = 3.6432 (5) Å

c = 6.6887 (7) Å

β = 111.669 (6)°

V = 211.87 (4) Å3

Z = 2

Mo Kα radiation

μ = 5.10 mm−1

T = 298 K

0.29 × 0.22 × 0.14 mm

Data collection

Enraf–Nonius CAD4 diffractometer

Absorption correction: ψ scan (North et al., 1968 ▶) T min = 0.274, T max = 0.498

876 measured reflections

354 independent reflections

350 reflections with I > 2σ(I)

R int = 0.018

2 standard reflections every 120 min intensity decay: 1.1%

Refinement

R[F 2 > 2σ(F 2)] = 0.018

wR(F 2) = 0.052

S = 1.16

354 reflections

30 parameters

Δρmax = 0.90 e Å−3

Δρmin = −0.57 e Å−3

Data collection: CAD-4 EXPRESS (Duisenberg, 1992 ▶; Macíček & Yordanov, 1992 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536813022411/ru2052sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813022411/ru2052Isup2.hkl

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

LiMoVO6	F(000) = 232
Mr = 249.82	Dx = 3.916 Mg m−3
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 25 reflections
a = 9.3555 (9) Å	θ = 11–16°
b = 3.6432 (5) Å	µ = 5.10 mm−1
c = 6.6887 (7) Å	T = 298 K
β = 111.669 (6)°	Prism, yellow
V = 211.87 (4) Å3	0.29 × 0.22 × 0.14 mm
Z = 2

Enraf Nonius CAD4 diffractometer	350 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.018
Graphite monochromator	θmax = 30.0°, θmin = 3.3°
ω/2θ scans	h = −12→12
Absorption correction: ψ scan (North et al., 1968)	k = −5→1
Tmin = 0.274, Tmax = 0.498	l = −9→9
876 measured reflections	2 standard reflections every 120 min
354 independent reflections	intensity decay: 1.1%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.018	w = 1/[σ2(Fo2) + (0.0273P)2 + 0.9791P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.052	(Δ/σ)max < 0.001
S = 1.16	Δρmax = 0.90 e Å−3
354 reflections	Δρmin = −0.57 e Å−3
30 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.008 (2)

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	Occ. (<1)
Mo	0.18622 (4)	0.0000	0.65068 (5)	0.00752 (17)	0.50
V	0.18622 (4)	0.0000	0.65068 (5)	0.00752 (17)	0.50
Li	0.0000	0.0000	0.0000	0.0152 (17)
O1	0.0259 (3)	0.0000	0.7107 (5)	0.0167 (5)
O2	0.3080 (3)	0.0000	0.4362 (4)	0.0096 (4)
O3	0.3319 (3)	0.0000	0.8860 (4)	0.0173 (5)

	U11	U22	U33	U12	U13	U23
Mo	0.0082 (2)	0.0049 (2)	0.0100 (2)	0.000	0.00406 (14)	0.000
V	0.0082 (2)	0.0049 (2)	0.0100 (2)	0.000	0.00406 (14)	0.000
Li	0.015 (4)	0.026 (5)	0.006 (3)	0.000	0.005 (3)	0.000
O1	0.0108 (10)	0.0092 (12)	0.0320 (14)	0.000	0.0102 (10)	0.000
O2	0.0118 (10)	0.0039 (10)	0.0159 (10)	0.000	0.0083 (8)	0.000
O3	0.0131 (11)	0.0221 (15)	0.0151 (11)	0.000	0.0032 (9)	0.000

Mo—O3	1.659 (3)	Li—O3vi	2.3423 (16)
Mo—O1	1.690 (3)	Li—O3i	2.3423 (16)
Mo—O2i	1.9189 (8)	O1—Livii	2.037 (3)
Mo—O2ii	1.9189 (8)	O1—Moiii	2.497 (3)
Mo—O2	2.136 (2)	O2—Vi	1.9189 (8)
Mo—O1iii	2.497 (3)	O2—Moi	1.9189 (8)
Li—O1iv	2.037 (3)	O2—Vii	1.9189 (8)
Li—O1iii	2.037 (3)	O2—Moii	1.9189 (8)
Li—O3ii	2.3423 (16)	O3—Liviii	2.3423 (16)
Li—O3v	2.3423 (16)	O3—Liix	2.3423 (16)
O3—Mo—O1	105.39 (14)	O3ii—Li—O3vi	77.90 (10)
O3—Mo—O2i	100.50 (8)	O3v—Li—O3vi	102.10 (10)
O1—Mo—O2i	101.46 (7)	O1iv—Li—O3i	90.48 (8)
O3—Mo—O2ii	100.50 (8)	O1iii—Li—O3i	89.52 (8)
O1—Mo—O2ii	101.46 (7)	O3ii—Li—O3i	102.10 (10)
O2i—Mo—O2ii	143.35 (14)	O3v—Li—O3i	77.90 (10)
O3—Mo—O2	100.49 (11)	O3vi—Li—O3i	180.00 (14)
O1—Mo—O2	154.13 (13)	Mo—O1—Livii	130.75 (16)
O2i—Mo—O2	73.43 (7)	Mo—O1—Moiii	103.17 (14)
O2ii—Mo—O2	73.43 (7)	Livii—O1—Moiii	126.08 (11)
O3—Mo—O1iii	177.79 (11)	Vi—O2—Moi	0.00 (2)
O1—Mo—O1iii	76.83 (14)	Vi—O2—Vii	143.35 (14)
O2i—Mo—O1iii	78.93 (8)	Moi—O2—Vii	143.35 (14)
O2ii—Mo—O1iii	78.93 (8)	Vi—O2—Moii	143.35 (14)
O2—Mo—O1iii	77.30 (9)	Moi—O2—Moii	143.35 (14)
O1iv—Li—O1iii	180.00 (14)	Vii—O2—Moii	0.00 (2)
O1iv—Li—O3ii	90.48 (8)	Vi—O2—Mo	106.57 (7)
O1iii—Li—O3ii	89.52 (8)	Moi—O2—Mo	106.57 (7)
O1iv—Li—O3v	89.52 (8)	Vii—O2—Mo	106.57 (7)
O1iii—Li—O3v	90.48 (8)	Moii—O2—Mo	106.57 (7)
O3ii—Li—O3v	180.00 (14)	Mo—O3—Liviii	121.78 (8)
O1iv—Li—O3vi	89.52 (8)	Mo—O3—Liix	121.78 (8)
O1iii—Li—O3vi	90.48 (8)	Liviii—O3—Liix	102.10 (10)