Penta-cobalt(II) divanadium(III) tetrakis(diphosphate), Co5V2(P2O7)4.

Co5V2(P2O7)4 was crystallized by chemical vapour transport using HCl as transport agent. Its crystal structure is isotypic to that of Fe(II) 5Fe(III) 2(P2O7)4 and can be regarded as a member of the thortveitite structure family with corrugated layers of metal-oxygen polyhedra extending parallel to (010). Significant occupational disorder between cobalt(II) and vanadium(III) is observed. Four of the five cation sites are occupied by both cobalt and vanadium. The fifth cation site (Co1) is occupied by cobalt only. Sites Co1, M3 and M4 are located on twofold axes. Sites Co1, M2, M3 and M4 show o-cta-hedral coordination by oxygen; M5 has a square-pyramidal environment.

Related literature

For related structures, see: Cruickshank et al. (1962 ▶); Gossner & Mussgnug (1929 ▶); Krishnamachari & Calvo (1972 ▶); Litterscheid (2009 ▶); Malaman et al. (1992 ▶); Palkina et al. (1985 ▶); Stefanidis & Nord (1984 ▶); Zachariasen (1930 ▶). For the preparation, see: Binnewies et al. (2012 ▶); Litterscheid (2009 ▶).

Experimental

Crystal data

Co5V2(P2O7)4

M = 1092.29

Orthorhombic,

a = 8.3551 (4) Å

b = 9.7067 (5) Å

c = 23.8555 (11) Å

V = 1934.69 (16) Å3

Z = 4

Mo Kα radiation

μ = 5.92 mm−1

T = 293 K

0.08 × 0.08 × 0.08 mm

Data collection

Stoe IPDS 2T diffractometer

Absorption correction: multi-scan (Blessing, 1995 ▶) T min = 0.495, T max = 0.647

9445 measured reflections

3800 independent reflections

2832 reflections with I > 2σ(I)

R int = 0.082

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.110

S = 0.92

3800 reflections

201 parameters

1 restraint

Δρmax = 1.02 e Å−3

Δρmin = −1.17 e Å−3

Absolute structure: Flack (1983 ▶), 2275 Friedel pairs

Flack parameter: −0.02 (2)

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813008507/br2223sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813008507/br2223Isup2.hkl

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

Co5V2(P2O7)4	F(000) = 2100
Mr = 1092.29	Dx = 3.75 Mg m−3
Orthorhombic, C2221	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 4330 reflections
a = 8.3551 (4) Å	θ = 1.0–29.1°
b = 9.7067 (5) Å	µ = 5.92 mm−1
c = 23.8555 (11) Å	T = 293 K
V = 1934.69 (16) Å3	Isometric, pink
Z = 4	0.08 × 0.08 × 0.08 mm

Stoe IPDS 2T 2-circle goniometer diffractometer	3800 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2832 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.082
profile data from θ/2θ scans	θmax = 34.1°, θmin = 3.6°
Absorption correction: multi-scan (Blessing, 1995)	h = −12→12
Tmin = 0.495, Tmax = 0.647	k = −13→15
9445 measured reflections	l = −28→35

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	w = 1/[σ2(Fo2) + (0.0575P)2] where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.046	(Δ/σ)max = 0.058
wR(F2) = 0.110	Δρmax = 1.02 e Å−3
S = 0.92	Δρmin = −1.17 e Å−3
3800 reflections	Extinction correction: SHELXL97 (Sheldrick, 2008)
201 parameters	Extinction coefficient: 0.00114 (15)
1 restraint	Absolute structure: Flack (1983), 2275 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.02 (2)

Experimental. To reach the desired data resolution with the given experimental setup the image plate had been tilted by 15 degrees. This is also the explanation for the asymmetrie in the upper and lower limits of observed hkl values.

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)
Co1	−0.08177 (13)	0	−0.5	0.0231 (3)
Co2	−0.06997 (9)	−0.35558 (9)	−0.38065 (4)	0.01028 (16)	0.3452 (5)
V2	−0.06997 (9)	−0.35558 (9)	−0.38065 (4)	0.01028 (16)	0.6548 (5)
Co3	0.29241 (13)	0	−0.5	0.0162 (3)	0.934 (19)
V3	0.29241 (13)	0	−0.5	0.0162 (3)	0.066 (19)
Co4	0	−0.71981 (12)	−0.25	0.0106 (3)	0.72 (2)
V4	0	−0.71981 (12)	−0.25	0.0106 (3)	0.28 (2)
Co5	0.31161 (9)	−0.36011 (9)	−0.35848 (4)	0.0146 (2)	0.827 (12)
V5	0.31161 (9)	−0.36011 (9)	−0.35848 (4)	0.0146 (2)	0.173 (12)
P1	0.09658 (15)	−0.29386 (13)	−0.49912 (6)	0.0084 (2)
P2	0.11867 (16)	−0.05623 (14)	−0.37555 (6)	0.0088 (3)
P3	0.10814 (15)	−0.64697 (13)	−0.37996 (6)	0.0075 (2)
P4	0.23708 (16)	−0.46167 (13)	−0.23058 (6)	0.0088 (2)
O1	0.1176 (4)	−0.4895 (4)	−0.37362 (15)	0.0091 (7)
O2	0.1166 (5)	−0.2135 (4)	−0.37347 (17)	0.0128 (7)
O3	0.1028 (4)	−0.1378 (4)	−0.49593 (17)	0.0119 (7)
O4	0.1778 (5)	−0.5885 (4)	−0.25902 (18)	0.0148 (8)
O5	0.0296 (5)	−0.3310 (4)	−0.55996 (17)	0.0161 (8)
O6	−0.2299 (4)	−0.5048 (4)	−0.40502 (16)	0.0119 (7)
O7	−0.1713 (4)	−0.8684 (4)	−0.27171 (17)	0.0121 (7)
O8	−0.0110 (5)	−0.7125 (4)	−0.33991 (17)	0.0144 (8)
O9	0.1241 (4)	−0.0051 (4)	−0.31260 (17)	0.0138 (7)
O10	−0.0396 (4)	−0.3561 (4)	−0.46426 (16)	0.0116 (7)
O11	−0.2444 (5)	0.1430 (5)	−0.48668 (19)	0.0174 (8)
O12	0.4680 (4)	−0.4907 (5)	−0.39934 (16)	0.0132 (7)
O13	−0.2302 (5)	−0.2113 (4)	−0.38130 (18)	0.0131 (7)
O14	0.1101 (5)	−0.3849 (4)	−0.19772 (17)	0.0132 (7)

	U11	U22	U33	U12	U13	U23
Co1	0.0073 (4)	0.0060 (4)	0.0559 (9)	0	0	−0.0023 (5)
Co2	0.0092 (3)	0.0085 (3)	0.0131 (4)	0.0004 (3)	−0.0003 (3)	0.0004 (3)
V2	0.0092 (3)	0.0085 (3)	0.0131 (4)	0.0004 (3)	−0.0003 (3)	0.0004 (3)
Co3	0.0109 (5)	0.0116 (5)	0.0260 (7)	0	0	−0.0022 (5)
V3	0.0109 (5)	0.0116 (5)	0.0260 (7)	0	0	−0.0022 (5)
Co4	0.0102 (5)	0.0075 (5)	0.0140 (6)	0	0.0005 (4)	0
V4	0.0102 (5)	0.0075 (5)	0.0140 (6)	0	0.0005 (4)	0
Co5	0.0118 (3)	0.0124 (4)	0.0197 (4)	−0.0005 (3)	0.0000 (3)	−0.0020 (3)
V5	0.0118 (3)	0.0124 (4)	0.0197 (4)	−0.0005 (3)	0.0000 (3)	−0.0020 (3)
P1	0.0081 (5)	0.0056 (5)	0.0114 (6)	0.0001 (4)	0.0015 (5)	0.0001 (5)
P2	0.0078 (5)	0.0064 (5)	0.0123 (7)	−0.0010 (4)	−0.0001 (5)	−0.0002 (5)
P3	0.0081 (5)	0.0043 (5)	0.0100 (5)	0.0012 (5)	−0.0004 (5)	0.0004 (5)
P4	0.0086 (6)	0.0070 (5)	0.0107 (6)	−0.0016 (4)	0.0009 (5)	0.0008 (4)
O1	0.0080 (14)	0.0060 (15)	0.0132 (18)	0.0023 (14)	0.0035 (14)	0.0015 (14)
O2	0.0141 (16)	0.0110 (17)	0.0133 (19)	−0.0008 (15)	0.0011 (16)	0.0030 (15)
O3	0.0112 (16)	0.0081 (15)	0.0162 (18)	0.0030 (14)	−0.0014 (16)	0.0017 (16)
O4	0.0163 (18)	0.0109 (17)	0.017 (2)	−0.0048 (15)	0.0022 (16)	−0.0004 (15)
O5	0.0145 (18)	0.019 (2)	0.0147 (19)	−0.0017 (15)	0.0007 (16)	−0.0063 (16)
O6	0.0106 (15)	0.0094 (16)	0.0157 (18)	−0.0007 (15)	0.0007 (14)	−0.0009 (14)
O7	0.0112 (15)	0.0103 (17)	0.0148 (18)	−0.0009 (14)	−0.0018 (14)	0.0043 (15)
O8	0.0179 (19)	0.0112 (18)	0.0142 (18)	−0.0027 (15)	−0.0001 (16)	−0.0004 (15)
O9	0.0102 (15)	0.0141 (17)	0.0171 (19)	−0.0014 (15)	0.0002 (14)	−0.0024 (16)
O10	0.0116 (16)	0.0128 (17)	0.0104 (17)	0.0014 (15)	0.0032 (14)	0.0001 (15)
O11	0.0107 (16)	0.0112 (17)	0.030 (2)	0.0046 (15)	0.0018 (16)	0.0011 (17)
O12	0.0080 (15)	0.0157 (18)	0.0158 (19)	−0.0022 (14)	0.0008 (14)	0.0036 (16)
O13	0.0114 (16)	0.0065 (16)	0.021 (2)	0.0020 (13)	−0.0019 (16)	−0.0014 (15)
O14	0.0122 (16)	0.0170 (19)	0.0102 (17)	0.0015 (15)	0.0014 (15)	−0.0011 (14)

Co1—O11	1.968 (4)	Co5—O12	2.065 (4)
Co1—O11i	1.968 (4)	Co5—O7iv	2.076 (4)
Co1—O3i	2.044 (4)	Co5—O1	2.082 (4)
Co1—O3	2.044 (4)	Co5—O8iv	2.109 (4)
Co2—O14ii	1.921 (4)	Co5—O2	2.192 (4)
Co2—O13	1.937 (4)	P1—O11v	1.493 (4)
Co2—O10	2.010 (4)	P1—O3	1.518 (4)
Co2—O1	2.043 (3)	P1—O10	1.533 (4)
Co2—O6	2.055 (4)	P1—O5	1.597 (4)
Co2—O2	2.089 (4)	P2—O12vi	1.520 (4)
Co3—O3i	2.075 (4)	P2—O2	1.527 (4)
Co3—O3	2.075 (4)	P2—O6iv	1.531 (4)
Co3—O10iii	2.156 (4)	P2—O9	1.582 (4)
Co3—O10iv	2.156 (4)	P3—O13v	1.489 (4)
Co3—O6iii	2.274 (4)	P3—O8	1.519 (4)
Co3—O6iv	2.274 (4)	P3—O1	1.538 (4)
Co4—O4ii	1.969 (4)	P3—O5vii	1.591 (4)
Co4—O4	1.969 (4)	P4—O4	1.490 (4)
Co4—O7	2.097 (4)	P4—O14	1.515 (4)
Co4—O7ii	2.097 (4)	P4—O7iv	1.539 (4)
Co4—O8	2.148 (4)	P4—O9viii	1.608 (4)
Co4—O8ii	2.148 (4)
O11—Co1—O11i	92.7 (3)	O11v—P1—O3	111.7 (2)
O11—Co1—O3i	93.86 (16)	O11v—P1—O10	113.0 (2)
O11i—Co1—O3i	167.12 (17)	O3—P1—O10	113.1 (2)
O11—Co1—O3	167.12 (17)	O11v—P1—O5	113.6 (2)
O11i—Co1—O3	93.86 (16)	O3—P1—O5	106.4 (2)
O3i—Co1—O3	82.0 (2)	O10—P1—O5	98.3 (2)
O14ii—Co2—O13	89.68 (18)	O12vi—P2—O2	114.9 (3)
O14ii—Co2—O10	170.85 (19)	O12vi—P2—O6iv	112.1 (2)
O13—Co2—O10	94.66 (17)	O2—P2—O6iv	110.5 (2)
O14ii—Co2—O1	87.68 (16)	O12vi—P2—O9	104.3 (2)
O13—Co2—O1	172.15 (17)	O2—P2—O9	106.4 (2)
O10—Co2—O1	89.03 (15)	O6iv—P2—O9	108.1 (2)
O14ii—Co2—O6	93.29 (17)	O13v—P3—O8	115.6 (2)
O13—Co2—O6	93.32 (16)	O13v—P3—O1	111.9 (2)
O10—Co2—O6	78.44 (16)	O8—P3—O1	112.8 (2)
O1—Co2—O6	94.22 (15)	O13v—P3—O5vii	107.4 (2)
O14ii—Co2—O2	98.53 (17)	O8—P3—O5vii	103.9 (2)
O13—Co2—O2	92.24 (16)	O1—P3—O5vii	104.1 (2)
O10—Co2—O2	89.36 (16)	O4—P4—O14	114.2 (2)
O1—Co2—O2	80.85 (15)	O4—P4—O7iv	111.2 (2)
O6—Co2—O2	166.96 (16)	O14—P4—O7iv	112.9 (2)
O3i—Co3—O3	80.5 (2)	O4—P4—O9viii	108.3 (2)
O3i—Co3—O10iii	153.63 (15)	O14—P4—O9viii	107.6 (2)
O3—Co3—O10iii	95.61 (15)	O7iv—P4—O9viii	101.8 (2)
O3i—Co3—O10iv	95.62 (15)	P3—O1—Co2	125.8 (2)
O3—Co3—O10iv	153.62 (15)	P3—O1—Co5	131.1 (2)
O10iii—Co3—O10iv	98.8 (2)	Co2—O1—Co5	103.14 (16)
O3i—Co3—O6iii	82.97 (15)	P2—O2—Co2	131.7 (3)
O3—Co3—O6iii	89.84 (15)	P2—O2—Co5	130.2 (2)
O10iii—Co3—O6iii	70.88 (14)	Co2—O2—Co5	98.01 (17)
O10iv—Co3—O6iii	115.74 (14)	P1—O3—Co1	128.7 (2)
O3i—Co3—O6iv	89.84 (15)	P1—O3—Co3	131.9 (2)
O3—Co3—O6iv	82.97 (15)	Co1—O3—Co3	98.73 (16)
O10iii—Co3—O6iv	115.73 (14)	P4—O4—Co4	137.3 (3)
O10iv—Co3—O6iv	70.88 (14)	P3vii—O5—P1	134.8 (3)
O6iii—Co3—O6iv	170.60 (19)	P2ix—O6—Co2	129.6 (2)
O4ii—Co4—O4	99.4 (3)	P2ix—O6—Co3ix	122.1 (2)
O4ii—Co4—O7	87.52 (17)	Co2—O6—Co3ix	102.37 (16)
O4—Co4—O7	158.93 (16)	P2ix—O6—V3ix	122.1 (2)
O4ii—Co4—O7ii	158.93 (16)	Co2—O6—V3ix	102.37 (16)
O4—Co4—O7ii	87.52 (17)	P4ix—O7—V5ix	128.6 (2)
O7—Co4—O7ii	93.1 (2)	P4ix—O7—Co5ix	128.6 (2)
O4ii—Co4—O8	93.18 (17)	P4ix—O7—Co4	125.9 (2)
O4—Co4—O8	84.36 (17)	V5ix—O7—Co4	105.46 (17)
O7—Co4—O8	75.35 (15)	Co5ix—O7—Co4	105.46 (17)
O7ii—Co4—O8	107.37 (16)	P3—O8—V5ix	127.8 (2)
O4ii—Co4—O8ii	84.36 (17)	P3—O8—Co5ix	127.8 (2)
O4—Co4—O8ii	93.18 (17)	P3—O8—Co4	127.9 (2)
O7—Co4—O8ii	107.37 (16)	V5ix—O8—Co4	102.55 (18)
O7ii—Co4—O8ii	75.35 (15)	Co5ix—O8—Co4	102.55 (18)
O8—Co4—O8ii	176.2 (2)	P2—O9—P4x	135.3 (3)
O12—Co5—O7iv	113.79 (16)	P1—O10—Co2	129.1 (2)
O12—Co5—O1	92.30 (15)	P1—O10—V3ix	121.6 (2)
O7iv—Co5—O1	101.71 (15)	Co2—O10—V3ix	108.17 (17)
O12—Co5—O8iv	94.11 (16)	P1—O10—Co3ix	121.6 (2)
O7iv—Co5—O8iv	76.62 (15)	Co2—O10—Co3ix	108.17 (17)
O1—Co5—O8iv	173.51 (15)	P1vi—O11—Co1	150.7 (3)
O12—Co5—O2	142.34 (16)	P2v—O12—Co5	127.2 (2)
O7iv—Co5—O2	103.80 (15)	P3vi—O13—Co2	158.5 (3)
O1—Co5—O2	77.59 (14)	P4—O14—V2ii	134.3 (3)
O8iv—Co5—O2	96.63 (16)	P4—O14—Co2ii	134.3 (3)