NASICON-type Na(3)V(2)(PO(4))(3).

Single crystals of the title compound, tris-odium divanadium(III) tris-(orthophosphate), were grown from a self-flux in the system Na(4)P(2)O(7)-NaVP(2)O(7). Na(3)V(2)(PO(4))(3) belongs to the family of NASICON-related structures and is built up from isolated [VO(6)] octa-hedra (3. symmetry) and [PO(4)] tetra-hedra (.2 symmetry) inter-linked via corners to establish the framework anion [V(2)(PO(4))(3)](3-). The two independent Na(+) cations are partially occupied [site-occupancy factors = 0.805 (18) and 0.731 (7)] and are located in channels with two different oxygen environments, viz sixfold coordination for the first (. symmetry) and eightfold for the second (.2 symmetry) Na(+) cation.

Related literature

For structures and properties of complex phosphates with general formula Na3 M III 2(PO4)3 (M III = Sc, Fe, Cr), see: Collin et al. (1986 ▶); Genkina et al. (1991 ▶); Lazoryak et al. (1980 ▶); Lucazeau et al. (1986 ▶); Masquelier et al. (1992 ▶); Susman et al. (1983 ▶). For preparation of NaVP2O7 which was used as an educt for crystal growth of the title compound, see: Zatovsky et al. (1999 ▶).

Experimental

Crystal data

Na3V2(PO4)3

M = 455.76

Trigonal,

a = 8.7288 (2) Å

c = 21.8042 (7) Å

V = 1438.73 (7) Å3

Z = 6

Mo Kα radiation

μ = 2.66 mm−1

T = 293 K

0.20 × 0.15 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur-3 CCD diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.635, T max = 0.780

12580 measured reflections

1331 independent reflections

1153 reflections with I > 2σ(I)

R int = 0.063

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.075

S = 1.1

1331 reflections

37 parameters

Δρmax = 1.12 e Å−3

Δρmin = −0.74 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 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, 1999 ▶) and enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810002801/wm2293sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002801/wm2293Isup2.hkl

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

Na3V2(PO4)3	Dx = 3.156 Mg m−3
Mr = 455.76	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3c	Cell parameters from 12580 reflections
Hall symbol: -R 3 2"c	θ = 3.3–45.0°
a = 8.7288 (2) Å	µ = 2.66 mm−1
c = 21.8042 (7) Å	T = 293 K
V = 1438.73 (7) Å3	Prism, green
Z = 6	0.20 × 0.15 × 0.10 mm
F(000) = 1320

Oxford Diffraction Xcalibur-3 CCD diffractometer	1331 independent reflections
Radiation source: fine-focus sealed tube	1153 reflections with I > 2σ(I)
graphite	Rint = 0.063
φ and ω scans	θmax = 45°, θmin = 3.3°
Absorption correction: multi-scan (Blessing, 1995)	h = −17→16
Tmin = 0.635, Tmax = 0.780	k = −17→17
12580 measured reflections	l = −43→41

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)] = 0.032	w = 1/[σ2(Fo2) + (0.0264P)2 + 5.1429P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.075	(Δ/σ)max < 0.001
S = 1.1	Δρmax = 1.12 e Å−3
1331 reflections	Δρmin = −0.73 e Å−3
37 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008)
0 restraints	Extinction coefficient: 0.0056 (4)

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)
V1	0.3333	0.6667	0.019498 (13)	0.00690 (6)
Na1	0.3333	0.6667	0.1667	0.149 (5)	0.805 (18)
Na2	0.6667	0.96726 (19)	0.0833	0.0522 (10)	0.731 (7)
P1	−0.04273 (5)	0.3333	0.0833	0.00866 (8)
O1	0.14193 (13)	0.49765 (14)	0.07762 (5)	0.01643 (16)
O2	0.54047 (16)	0.84480 (17)	−0.02643 (7)	0.0259 (2)

	U11	U22	U33	U12	U13	U23
V1	0.00643 (7)	0.00643 (7)	0.00784 (10)	0.00321 (4)	0	0
Na1	0.218 (8)	0.218 (8)	0.0111 (14)	0.109 (4)	0	0
Na2	0.0224 (8)	0.0170 (5)	0.119 (2)	0.0112 (4)	−0.0354 (11)	−0.0177 (5)
P1	0.00635 (10)	0.00714 (14)	0.01276 (15)	0.00357 (7)	0.00152 (5)	0.00305 (11)
O1	0.0089 (3)	0.0130 (3)	0.0220 (4)	0.0015 (3)	0.0048 (3)	0.0057 (3)
O2	0.0185 (4)	0.0223 (5)	0.0322 (6)	0.0067 (4)	0.0143 (4)	0.0151 (4)

V1—O2i	1.9693 (10)	Na2—O1ii	2.3883 (12)
V1—O2	1.9693 (11)	Na2—O1vi	2.3883 (12)
V1—O2ii	1.9693 (10)	Na2—O1i	2.4448 (19)
V1—O1ii	2.0271 (9)	Na2—O1vii	2.4449 (19)
V1—O1	2.0271 (9)	Na2—O2viii	2.6280 (16)
V1—O1i	2.0271 (9)	Na2—O2	2.6281 (16)
V1—Na2i	3.1070 (6)	Na2—O2ix	2.8352 (19)
V1—Na2	3.1070 (7)	Na2—O2x	2.8352 (19)
V1—Na2ii	3.1070 (6)	Na2—P1xi	2.9222 (11)
V1—Na1	3.2096 (3)	Na2—P1ii	2.9222 (11)
Na1—O1	2.5045 (11)	Na2—P1i	2.9968 (17)
Na1—O1ii	2.5045 (11)	P1—O2xii	1.5227 (12)
Na1—O1i	2.5045 (11)	P1—O2xiii	1.5227 (12)
Na1—O1iii	2.5045 (11)	P1—O1	1.5358 (10)
Na1—O1iv	2.5045 (11)	P1—O1xiv	1.5359 (10)
Na1—O1v	2.5046 (11)	P1—Na2xv	2.9222 (11)
Na1—V1iv	3.2081 (2)	P1—Na2i	2.9222 (11)
Na1—Na2i	3.3193 (6)	P1—Na2ii	2.9968 (17)
Na1—Na2v	3.3193 (6)	O1—Na2i	2.3883 (12)
Na1—Na2	3.3193 (6)	O1—Na2ii	2.4448 (19)
Na1—Na2ii	3.3205 (6)
O2i—V1—O2	96.44 (6)	O1ii—Na2—O2	68.20 (4)
O2i—V1—O2ii	96.44 (6)	O1vi—Na2—O2	115.98 (4)
O2—V1—O2ii	96.44 (6)	O1i—Na2—O2	66.40 (4)
O2i—V1—O1ii	88.22 (5)	O1vii—Na2—O2	93.51 (6)
O2—V1—O1ii	89.72 (5)	O2viii—Na2—O2	157.25 (9)
O2ii—V1—O1ii	171.80 (6)	O1ii—Na2—O2ix	54.99 (4)
O2i—V1—O1	89.72 (5)	O1vi—Na2—O2ix	108.39 (6)
O2—V1—O1	171.80 (6)	O1i—Na2—O2ix	115.94 (4)
O2ii—V1—O1	88.22 (5)	O1vii—Na2—O2ix	151.11 (4)
O1ii—V1—O1	85.05 (5)	O2viii—Na2—O2ix	85.67 (3)
O2i—V1—O1i	171.80 (6)	O2—Na2—O2ix	112.13 (5)
O2—V1—O1i	88.22 (5)	O1ii—Na2—O2x	108.39 (6)
O2ii—V1—O1i	89.72 (5)	O1vi—Na2—O2x	54.99 (4)
O1ii—V1—O1i	85.05 (5)	O1i—Na2—O2x	151.10 (4)
O1—V1—O1i	85.05 (5)	O1vii—Na2—O2x	115.94 (4)
O1—Na1—O1ii	66.33 (3)	O2viii—Na2—O2x	112.13 (5)
O1—Na1—O1i	66.33 (3)	O2—Na2—O2x	85.67 (3)
O1ii—Na1—O1i	66.33 (3)	O2ix—Na2—O2x	80.45 (7)
O1—Na1—O1iii	113.67 (3)	O2xii—P1—O2xiii	111.67 (12)
O1ii—Na1—O1iii	180	O2xii—P1—O1	106.07 (7)
O1i—Na1—O1iii	113.67 (3)	O2xiii—P1—O1	112.18 (7)
O1—Na1—O1iv	180	O2xii—P1—O1xiv	112.19 (7)
O1ii—Na1—O1iv	113.67 (3)	O2xiii—P1—O1xiv	106.07 (7)
O1i—Na1—O1iv	113.67 (3)	O1—P1—O1xiv	108.74 (9)
O1iii—Na1—O1iv	66.33 (3)	P1—O1—V1	145.95 (7)
O1—Na1—O1v	113.67 (3)	P1—O1—Na2i	93.73 (6)
O1ii—Na1—O1v	113.67 (3)	V1—O1—Na2i	89.05 (5)
O1i—Na1—O1v	180	P1—O1—Na2ii	94.93 (5)
O1iii—Na1—O1v	66.33 (3)	V1—O1—Na2ii	87.50 (4)
O1iv—Na1—O1v	66.33 (3)	Na2i—O1—Na2ii	169.09 (5)
O1ii—Na2—O1vi	160.52 (9)	P1—O1—Na1	124.53 (6)
O1ii—Na2—O1i	69.07 (5)	V1—O1—Na1	89.52 (4)
O1vi—Na2—O1i	130.40 (6)	Na2i—O1—Na1	85.40 (5)
O1ii—Na2—O1vii	130.40 (6)	Na2ii—O1—Na1	84.23 (4)
O1vi—Na2—O1vii	69.07 (5)	P1xvi—O2—V1	151.38 (10)
O1i—Na2—O1vii	61.41 (6)	P1xvi—O2—Na2	120.77 (8)
O1ii—Na2—O2viii	115.98 (4)	V1—O2—Na2	83.72 (5)
O1vi—Na2—O2viii	68.20 (4)	P1xvi—O2—Na2xvii	77.85 (5)
O1i—Na2—O2viii	93.51 (6)	V1—O2—Na2xvii	107.30 (6)
O1vii—Na2—O2viii	66.40 (4)	Na2—O2—Na2xvii	113.64 (7)

Table 1

Selected bond lengths (Å)

V1—O2i	1.9693 (10)
V1—O1ii	2.0271 (9)
Na1—O1	2.5045 (11)
Na2—O1ii	2.3883 (12)
Na2—O1i	2.4448 (19)
Na2—O2iii	2.6280 (16)
Na2—O2iv	2.8352 (19)
P1—O2v	1.5227 (12)
P1—O1	1.5358 (10)

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