Sodium trivanadium(III) bis­(sulfate) hexa­hydro­xide

The title compound, NaV₃(SO₄)₂(OH)₆, was synthesized and found to crystallize in the trigonal space group Rm with the Na atom at a site with 3m symmetry, the V atom at a site with 2/m symmetry, and the S and a terminal O atom at sites with 3m symmetry; the remaining two O atoms and the H atom are at sites with m symmetry. Octahedrally coordinated vanadium and tetrahedral sulfate ions share corners to form layers that are held together by hydrogen bonds and by sodium ions, which are located between the layers.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997) and ATOMS (Dowty, 1999); software used to prepare material for publication: SHELXL97.

Sodium trivanadium disulfate hexahydroxide

Crystal data

NaV3(SO4)2(OH)6	Dx = 3.018 Mg m^−3
Mr = 470	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3m	Cell parameters from 1353 reflections
Hall symbol: -R 3 2"	θ = 6.9–56.9°
a = 7.2821 (6) Å	µ = 3.19 mm^−1
c = 16.889 (2) Å	T = 293 K
V = 775.6 (2) Å^3	Octahedron, brown
Z = 3	0.13 × 0.12 × 0.06 mm
F(000) = 690

Data collection

CCD Smart Apex diffractometer	272 independent reflections
Radiation source: fine-focus sealed tube	265 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.024
ω scans	θmax = 28.5°, θmin = 3.5°
Absorption correction: ψ scan (SADABS; Sheldrick, 1996)	h = −9→9
Tmin = 0.583, Tmax = 0.790	k = −9→8
1643 measured reflections	l = −22→11

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.026	Hydrogen site location: difference Fourier map
wR(F^2) = 0.072	All H-atom parameters refined
S = 1.31	w = 1/[σ^2(Fo^2) + (0.0325P)^2 + 3.007P] where P = (Fo^2 + 2Fc^2)/3
272 reflections	(Δ/σ)max < 0.001
27 parameters	Δρmax = 0.67 e Å^−3
0 restraints	Δρmin = −0.50 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Na1	0.0000	0.0000	0.0000	0.0715 (19)
V1	0.8333	0.1667	0.1667	0.0081 (3)
S1	0.6667	0.3333	0.02351 (7)	0.0076 (3)
O1	1.12675 (18)	0.2535 (4)	0.13318 (13)	0.0117 (5)
O2	0.77717 (17)	0.22283 (17)	0.05270 (12)	0.0131 (5)
O3	0.6667	0.3333	−0.0627 (2)	0.0121 (8)
H1	1.167 (3)	0.334 (6)	0.114 (3)	0.015*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Na1	0.094 (3)	0.094 (3)	0.027 (2)	0.0469 (16)	0.000	0.000
V1	0.0076 (3)	0.0076 (3)	0.0102 (4)	0.0046 (3)	−0.00007 (12)	0.00007 (12)
S1	0.0084 (4)	0.0084 (4)	0.0061 (5)	0.00418 (19)	0.000	0.000
O1	0.0086 (7)	0.0101 (11)	0.0168 (10)	0.0050 (6)	0.0030 (4)	0.0060 (9)
O2	0.0170 (8)	0.0170 (8)	0.0109 (9)	0.0127 (9)	−0.0006 (4)	0.0006 (4)
O3	0.0153 (11)	0.0153 (11)	0.0057 (15)	0.0077 (6)	0.000	0.000

Geometric parameters (Å, º)

Na1—O1^i	2.760 (2)	V1—O1^viii	1.9835 (9)
Na1—O1^ii	2.760 (2)	V1—O1^ix	1.9835 (9)
Na1—O1^iii	2.760 (2)	V1—O2	2.051 (2)
Na1—O1^iv	2.760 (2)	V1—O2^ix	2.051 (2)
Na1—O1^v	2.760 (2)	V1—Na1^x	3.5132 (3)
Na1—O1^vi	2.760 (2)	V1—Na1^xi	3.5133 (3)
Na1—O2^iii	2.948 (2)	S1—O3	1.457 (4)
Na1—O2^iv	2.948 (2)	S1—O2	1.478 (2)
Na1—O2^vi	2.948 (2)	S1—O2^xii	1.478 (2)
Na1—O2^v	2.948 (2)	S1—O2^iii	1.478 (2)
Na1—O2^i	2.948 (2)	O1—V1^xiii	1.9835 (9)
Na1—O2^ii	2.948 (2)	O1—Na1^x	2.760 (2)
V1—O1^vii	1.9835 (9)	O2—Na1^x	2.948 (2)
V1—O1	1.9835 (9)
O1^i—Na1—O1^ii	180.00 (5)	O2^vi—Na1—O2^i	68.70 (4)
O1^i—Na1—O1^iii	60.23 (8)	O2^v—Na1—O2^i	111.30 (4)
O1^ii—Na1—O1^iii	119.77 (8)	O1^i—Na1—O2^ii	121.48 (3)
O1^i—Na1—O1^iv	119.77 (8)	O1^ii—Na1—O2^ii	58.52 (3)
O1^ii—Na1—O1^iv	60.23 (8)	O1^iii—Na1—O2^ii	72.17 (6)
O1^iii—Na1—O1^iv	180.00 (7)	O1^iv—Na1—O2^ii	107.83 (6)
O1^i—Na1—O1^v	60.23 (8)	O1^v—Na1—O2^ii	121.48 (3)
O1^ii—Na1—O1^v	119.77 (8)	O1^vi—Na1—O2^ii	58.52 (3)
O1^iii—Na1—O1^v	60.23 (8)	O2^iii—Na1—O2^ii	68.70 (4)
O1^iv—Na1—O1^v	119.77 (8)	O2^iv—Na1—O2^ii	111.30 (4)
O1^i—Na1—O1^vi	119.77 (8)	O2^vi—Na1—O2^ii	111.30 (4)
O1^ii—Na1—O1^vi	60.23 (8)	O2^v—Na1—O2^ii	68.70 (4)
O1^iii—Na1—O1^vi	119.77 (8)	O2^i—Na1—O2^ii	180.00 (3)
O1^iv—Na1—O1^vi	60.23 (8)	O1^vii—V1—O1	88.55 (13)
O1^v—Na1—O1^vi	180.00 (5)	O1^vii—V1—O1^viii	180.0
O1^i—Na1—O2^iii	58.52 (3)	O1—V1—O1^viii	91.45 (13)
O1^ii—Na1—O2^iii	121.48 (3)	O1^vii—V1—O1^ix	91.45 (13)
O1^iii—Na1—O2^iii	58.52 (3)	O1—V1—O1^ix	180.0
O1^iv—Na1—O2^iii	121.48 (3)	O1^viii—V1—O1^ix	88.55 (13)
O1^v—Na1—O2^iii	107.83 (6)	O1^vii—V1—O2	87.67 (7)
O1^vi—Na1—O2^iii	72.17 (6)	O1—V1—O2	87.67 (7)
O1^i—Na1—O2^iv	121.48 (3)	O1^viii—V1—O2	92.33 (7)
O1^ii—Na1—O2^iv	58.52 (3)	O1^ix—V1—O2	92.33 (7)
O1^iii—Na1—O2^iv	121.48 (3)	O1^vii—V1—O2^ix	92.33 (7)
O1^iv—Na1—O2^iv	58.52 (3)	O1—V1—O2^ix	92.33 (7)
O1^v—Na1—O2^iv	72.17 (6)	O1^viii—V1—O2^ix	87.66 (7)
O1^vi—Na1—O2^iv	107.83 (6)	O1^ix—V1—O2^ix	87.66 (7)
O2^iii—Na1—O2^iv	180.00 (9)	O2—V1—O2^ix	180.0
O1^i—Na1—O2^vi	72.17 (6)	O1^vii—V1—Na1^x	51.58 (7)
O1^ii—Na1—O2^vi	107.83 (6)	O1—V1—Na1^x	51.58 (7)
O1^iii—Na1—O2^vi	121.48 (3)	O1^viii—V1—Na1^x	128.42 (7)
O1^iv—Na1—O2^vi	58.52 (3)	O1^ix—V1—Na1^x	128.42 (7)
O1^v—Na1—O2^vi	121.48 (3)	O2—V1—Na1^x	56.96 (6)
O1^vi—Na1—O2^vi	58.52 (3)	O2^ix—V1—Na1^x	123.04 (6)
O2^iii—Na1—O2^vi	68.70 (4)	O1^vii—V1—Na1^xi	128.42 (7)
O2^iv—Na1—O2^vi	111.30 (4)	O1—V1—Na1^xi	128.42 (7)
O1^i—Na1—O2^v	107.83 (6)	O1^viii—V1—Na1^xi	51.58 (7)
O1^ii—Na1—O2^v	72.17 (6)	O1^ix—V1—Na1^xi	51.58 (7)
O1^iii—Na1—O2^v	58.52 (3)	O2—V1—Na1^xi	123.04 (6)
O1^iv—Na1—O2^v	121.48 (3)	O2^ix—V1—Na1^xi	56.96 (6)
O1^v—Na1—O2^v	58.52 (3)	Na1^x—V1—Na1^xi	180.0
O1^vi—Na1—O2^v	121.48 (3)	O3—S1—O2	109.48 (9)
O2^iii—Na1—O2^v	111.30 (4)	O3—S1—O2^xii	109.48 (9)
O2^iv—Na1—O2^v	68.70 (4)	O2—S1—O2^xii	109.46 (9)
O2^vi—Na1—O2^v	180.0	O3—S1—O2^iii	109.48 (9)
O1^i—Na1—O2^i	58.52 (3)	O2—S1—O2^iii	109.46 (9)
O1^ii—Na1—O2^i	121.48 (3)	O2^xii—S1—O2^iii	109.46 (9)
O1^iii—Na1—O2^i	107.83 (6)	V1^xiii—O1—V1	133.23 (12)
O1^iv—Na1—O2^i	72.17 (6)	V1^xiii—O1—Na1^x	94.15 (7)
O1^v—Na1—O2^i	58.52 (3)	V1—O1—Na1^x	94.15 (7)
O1^vi—Na1—O2^i	121.48 (3)	S1—O2—V1	129.68 (13)
O2^iii—Na1—O2^i	111.30 (4)	S1—O2—Na1^x	142.95 (11)
O2^iv—Na1—O2^i	68.70 (4)	V1—O2—Na1^x	87.37 (7)

Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z; (iii) −x+y+1, −x+1, z; (iv) x−y−1, x−1, −z; (v) −y, x−y−1, z; (vi) y, −x+y+1, −z; (vii) −y+1, x−y−1, z; (viii) y+2/3, −x+y+4/3, −z+1/3; (ix) −x+5/3, −y+1/3, −z+1/3; (x) x+1, y, z; (xi) x+2/3, y+1/3, z+1/3; (xii) −y+1, x−y, z; (xiii) −x+y+2, −x+1, z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3^xiv	0.62 (4)	2.25 (4)	2.865 (3)	171 (6)

Symmetry code: (xiv) y+1, x, −z.