The synthetic cobalt vanadium selenite, Co₂V₂Se₂O₁₁.

The crystal structure of dicobalt(II) divanadium(V) disel-enium(IV) undeca-oxide, Co₂V₂Se₂O₁₁, exhibits a three-dimensional framework, the building units being distorted CoO₆ octa-hedra and VO₅ square pyramids arranged so as to form alternate chains along [010]. The framework has channels along [100] and [010] in which the two Ψ-SeO₃E (site symmetries m; E being the 4s² lone electron pair of Se(IV)) tetra-hedra reside and connect to the other building blocks. The structure contains corner- and edge-sharing CoO₆ octa-hedra, corner- and edge-sharing VO₅ square pyramids and edge-sharing Ψ-SeO₃E tetra-hedra. Co₂V₂Se₂O₁₁ is the first oxide containing all the cations Co(II), V(V) and Se(IV).

Related literature

For general background, including bond-valence-sum calculations, see: Brown & Altermatt (1985 ▶). For related structures, see: Allen et al. (2004 ▶); Becker et al. (2007 ▶); Jiang et al. (2008 ▶); Millet et al. (1999 ▶); Pitzschenke & Jansen (2007 ▶); Sauerbrei et al. (1974 ▶).

Experimental

Crystal data

Co2V2Se2O11

M = 553.66

Monoclinic,

a = 4.7913 (2) Å

b = 8.8680 (4) Å

c = 10.6156 (5) Å

β = 101.115 (5)°

V = 442.59 (3) Å3

Z = 2

Mo Kα radiation

μ = 14.01 mm−1

T = 292 K

0.05 × 0.03 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer

Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007 ▶), based on expressions derived by Clark & Reid (1995 ▶)] T min = 0.659, T max = 0.756

4219 measured reflections

1534 independent reflections

1023 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.048

S = 0.76

1534 reflections

85 parameters

Δρmax = 1.28 e Å−3

Δρmin = −0.98 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2001 ▶); software used to prepare material for publication: enCIFer (Allen et al., 2004 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027286/pk2421sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027286/pk2421Isup2.hkl

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

Co2V2Se2O11	F(000) = 512
Mr = 553.66	Dx = 4.155 Mg m−3
Monoclinic, P21/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yb	Cell parameters from 1387 reflections
a = 4.7913 (2) Å	θ = 3.9–32.2°
b = 8.8680 (4) Å	µ = 14.01 mm−1
c = 10.6156 (5) Å	T = 292 K
β = 101.115 (5)°	Block, red
V = 442.59 (3) Å3	0.05 × 0.03 × 0.02 mm
Z = 2

Oxford Diffraction Xcalibur Sapphire3 diffractometer	1534 independent reflections
Radiation source: fine-focus sealed tube	1023 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.051
Detector resolution: 16.5 pixels mm-1	θmax = 32.3°, θmin = 3.9°
ω scans	h = −7→7
Absorption correction: analytical [CrysAlis RED (Oxford Diffraction, 2007), based on expressions derived by Clark & Reid (1995)]	k = −11→12
Tmin = 0.659, Tmax = 0.756	l = −15→13
4219 measured reflections

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.032	Secondary atom site location: difference Fourier map
wR(F2) = 0.048	w = 1/[σ2(Fo2) + (0.0114P)2] where P = (Fo2 + 2Fc2)/3
S = 0.76	(Δ/σ)max = 0.001
1534 reflections	Δρmax = 1.28 e Å−3
85 parameters	Δρmin = −0.98 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
Se1	0.38839 (12)	0.2500	0.45047 (6)	0.00668 (13)
Se2	0.14374 (12)	0.2500	0.89926 (5)	0.00653 (13)
Co1	0.95757 (12)	0.42816 (6)	0.63219 (5)	0.00751 (13)
V1	0.53298 (15)	0.56239 (8)	0.85002 (6)	0.00660 (15)
O1	0.6860 (8)	0.2500	0.5658 (4)	0.0105 (9)
O6	0.7568 (6)	0.4597 (3)	0.7887 (3)	0.0118 (6)
O5	0.3738 (6)	0.4001 (3)	0.9523 (3)	0.0107 (6)
O2	0.2107 (6)	0.0989 (3)	0.4958 (3)	0.0093 (6)
O3	0.1701 (8)	0.2500	0.7454 (4)	0.0088 (9)
O4	0.2448 (6)	0.5786 (3)	0.7407 (3)	0.0132 (7)
O7	0.6843 (8)	0.7500	0.8501 (4)	0.0077 (9)

	U11	U22	U33	U12	U13	U23
Se1	0.0068 (3)	0.0069 (3)	0.0064 (3)	0.000	0.0014 (2)	0.000
Se2	0.0080 (3)	0.0051 (3)	0.0063 (3)	0.000	0.0008 (2)	0.000
Co1	0.0080 (3)	0.0063 (3)	0.0082 (3)	0.0001 (2)	0.0016 (2)	0.0001 (2)
V1	0.0078 (3)	0.0063 (3)	0.0058 (3)	−0.0003 (3)	0.0017 (3)	0.0000 (3)
O1	0.008 (2)	0.005 (2)	0.017 (2)	0.000	−0.0012 (18)	0.000
O6	0.0140 (16)	0.0077 (15)	0.0148 (16)	0.0010 (12)	0.0059 (13)	−0.0014 (12)
O5	0.0153 (16)	0.0113 (15)	0.0045 (14)	−0.0088 (12)	−0.0003 (12)	−0.0024 (11)
O2	0.0106 (15)	0.0103 (16)	0.0071 (15)	−0.0021 (12)	0.0021 (12)	−0.0024 (11)
O3	0.012 (2)	0.006 (2)	0.007 (2)	0.000	−0.0022 (17)	0.000
O4	0.0139 (16)	0.0101 (16)	0.0132 (16)	−0.0020 (12)	−0.0031 (13)	0.0025 (12)
O7	0.009 (2)	0.005 (2)	0.010 (2)	0.000	0.0024 (17)	0.000

Se1—O1	1.691 (4)	Co1—O6	2.093 (3)
Se1—O2	1.706 (3)	Co1—O4iv	2.095 (3)
Se1—O2i	1.706 (3)	Co1—O3iv	2.122 (3)
Se2—O3	1.663 (4)	V1—O4	1.630 (3)
Se2—O5	1.750 (3)	V1—O6	1.635 (3)
Se2—O5i	1.750 (3)	V1—O7	1.8147 (17)
Co1—O2ii	2.074 (3)	V1—O5	2.038 (3)
Co1—O1	2.081 (3)	V1—O5v	2.086 (3)
Co1—O2iii	2.090 (3)
O1—Se1—O2	101.12 (13)	O2ii—Co1—O3iv	91.59 (13)
O1—Se1—O2i	101.12 (13)	O1—Co1—O3iv	80.04 (12)
O2—Se1—O2i	103.52 (19)	O2iii—Co1—O3iv	172.01 (14)
O3—Se2—O5	98.85 (13)	O6—Co1—O3iv	83.90 (13)
O3—Se2—O5i	98.85 (13)	O4iv—Co1—O3iv	88.29 (11)
O5—Se2—O5i	98.97 (19)	O4—V1—O6	107.24 (15)
O2ii—Co1—O1	95.00 (14)	O4—V1—O7	101.71 (16)
O2ii—Co1—O2iii	80.44 (12)	O6—V1—O7	102.62 (15)
O1—Co1—O2iii	101.07 (12)	O4—V1—O5	95.11 (13)
O2ii—Co1—O6	171.78 (11)	O6—V1—O5	99.22 (13)
O1—Co1—O6	90.99 (14)	O7—V1—O5	146.92 (14)
O2iii—Co1—O6	103.94 (11)	O4—V1—O5v	133.61 (14)
O2ii—Co1—O4iv	92.69 (12)	O6—V1—O5v	117.38 (13)
O1—Co1—O4iv	166.17 (13)	O7—V1—O5v	81.09 (14)
O2iii—Co1—O4iv	91.51 (11)	O5—V1—O5v	66.81 (12)
O6—Co1—O4iv	80.34 (11)