A binuclear vanadium oxyfluoride: di-μ-oxido-bis-[(2,2'-bipyrid-yl)fluorido-oxidovanadium(V)].

The title compound, [V(2)F(2)O(4)(C(10)H(8)N)(2)], is a centrosymmetric binuclear vanadium(V) species with the metal ions in a distorted octa-hedral environment. The coordination geometries of the symmetry-equivalent V(V) atoms are defined by cis-terminal fluoride and oxide groups, unsymmetrically bridging oxide groups and the N-atom donors of the bipyridyl ligand. The crystal packing is stabilized by weak inter-molecular C-H⋯O and C-H⋯F hydrogen bonds.

Related literature

For oxyfluorido­molybdates and -­vanadates, see: Adil et al. (2010 ▶); Burkholder & Zubieta (2004 ▶); DeBurgomaster & Zubieta (2010 ▶); Jones et al. (2010 ▶); Michailovski et al. (2006 ▶, 2009 ▶).

Experimental

Crystal data

[V2F2O4(C10H8N)2]

M = 516.25

Monoclinic,

a = 9.7526 (6) Å

b = 12.6499 (8) Å

c = 16.023 (5) Å

β = 92.631 (5)°

V = 1974.7 (6) Å3

Z = 4

Mo Kα radiation

μ = 1.00 mm−1

T = 90 K

0.22 × 0.12 × 0.10 mm

Data collection

Bruker APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.866, T max = 0.905

9692 measured reflections

2406 independent reflections

2357 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.079

S = 1.13

2406 reflections

145 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.38 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: CrystalMaker (Palmer, 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810031302/om2351sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810031302/om2351Isup2.hkl

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

[V2F2O4(C10H8N)2]	F(000) = 1040.0
Mr = 516.25	Dx = 1.737 Mg m−3Dm = 1.74 (2) Mg m−3Dm measured by flotation
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 5752 reflections
a = 9.7526 (6) Å	θ = 2.6–28.3°
b = 12.6499 (8) Å	µ = 1.00 mm−1
c = 16.023 (5) Å	T = 90 K
β = 92.631 (5)°	Rod, yellow
V = 1974.7 (6) Å3	0.22 × 0.12 × 0.10 mm
Z = 4

Bruker APEX CCD area-detector diffractometer	2406 independent reflections
Radiation source: fine-focus sealed tube	2357 reflections with I > 2σ(I)
graphite	Rint = 0.018
Detector resolution: 512 pixels mm-1	θmax = 28.1°, θmin = 2.5°
φ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −16→16
Tmin = 0.866, Tmax = 0.905	l = −20→21
9692 measured reflections

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.079	H-atom parameters constrained
S = 1.13	w = 1/[σ2(Fo2) + (0.0314P)2 + 4.0741P] where P = (Fo2 + 2Fc2)/3
2406 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.38 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
V1	0.10805 (3)	1.04160 (2)	0.066763 (17)	0.01424 (10)
F1	−0.01010 (11)	1.03518 (8)	0.15020 (6)	0.0199 (2)
O1	0.21267 (13)	1.13285 (10)	0.10042 (8)	0.0205 (3)
O2	−0.01453 (12)	0.90041 (9)	0.01329 (7)	0.0133 (2)
N1	0.20945 (14)	0.90735 (11)	0.13175 (9)	0.0144 (3)
N2	0.25791 (14)	0.97955 (11)	−0.01525 (9)	0.0142 (3)
C1	0.17578 (18)	0.87555 (14)	0.20780 (11)	0.0176 (3)
H1	0.1106	0.9156	0.2367	0.021*
C2	0.23257 (18)	0.78627 (14)	0.24593 (11)	0.0183 (3)
H2	0.2056	0.7650	0.2996	0.022*
C3	0.32950 (18)	0.72849 (13)	0.20438 (11)	0.0185 (3)
H3	0.3696	0.6669	0.2290	0.022*
C4	0.36682 (18)	0.76235 (14)	0.12620 (11)	0.0180 (3)
H4	0.4339	0.7248	0.0969	0.022*
C5	0.30457 (16)	0.85198 (13)	0.09144 (10)	0.0137 (3)
C6	0.33609 (17)	0.89567 (13)	0.00892 (10)	0.0144 (3)
C7	0.44046 (17)	0.85774 (14)	−0.03932 (11)	0.0183 (3)
H7	0.4940	0.7985	−0.0214	0.022*
C8	0.46484 (17)	0.90815 (15)	−0.11414 (11)	0.0199 (4)
H8	0.5357	0.8839	−0.1481	0.024*
C9	0.38475 (18)	0.99419 (15)	−0.13875 (11)	0.0204 (4)
H9	0.4002	1.0299	−0.1896	0.024*
C10	0.28181 (18)	1.02718 (14)	−0.08794 (11)	0.0178 (3)
H10	0.2262	1.0856	−0.1052	0.021*

	U11	U22	U33	U12	U13	U23
V1	0.01400 (15)	0.01331 (15)	0.01525 (16)	0.00446 (10)	−0.00118 (10)	−0.00316 (10)
F1	0.0225 (5)	0.0227 (5)	0.0148 (5)	0.0086 (4)	0.0030 (4)	−0.0001 (4)
O1	0.0197 (6)	0.0188 (6)	0.0226 (6)	0.0028 (5)	−0.0028 (5)	−0.0063 (5)
O2	0.0146 (5)	0.0124 (5)	0.0129 (5)	0.0035 (4)	0.0002 (4)	−0.0001 (4)
N1	0.0134 (6)	0.0154 (6)	0.0140 (6)	0.0032 (5)	−0.0016 (5)	−0.0015 (5)
N2	0.0132 (6)	0.0160 (6)	0.0134 (7)	0.0011 (5)	−0.0001 (5)	−0.0018 (5)
C1	0.0180 (8)	0.0197 (8)	0.0150 (8)	0.0044 (6)	0.0000 (6)	−0.0017 (6)
C2	0.0207 (8)	0.0193 (8)	0.0145 (8)	0.0009 (6)	−0.0010 (6)	0.0004 (6)
C3	0.0218 (8)	0.0130 (7)	0.0201 (8)	0.0030 (6)	−0.0037 (7)	0.0003 (6)
C4	0.0183 (8)	0.0151 (8)	0.0207 (8)	0.0049 (6)	0.0006 (6)	−0.0015 (6)
C5	0.0128 (7)	0.0140 (7)	0.0139 (7)	0.0009 (6)	−0.0022 (6)	−0.0028 (6)
C6	0.0140 (7)	0.0140 (7)	0.0150 (8)	0.0002 (6)	−0.0014 (6)	−0.0033 (6)
C7	0.0152 (8)	0.0188 (8)	0.0208 (8)	0.0032 (6)	0.0011 (6)	−0.0033 (6)
C8	0.0151 (8)	0.0257 (9)	0.0192 (8)	0.0012 (7)	0.0040 (6)	−0.0050 (7)
C9	0.0182 (8)	0.0258 (9)	0.0173 (8)	−0.0005 (7)	0.0031 (6)	0.0015 (7)
C10	0.0161 (8)	0.0194 (8)	0.0178 (8)	0.0023 (6)	0.0001 (6)	0.0009 (6)

V1—O1	1.6167 (13)	C2—H2	0.9500
V1—O2i	1.7052 (12)	C3—C4	1.388 (3)
V1—F1	1.8064 (11)	C3—H3	0.9500
V1—N2	2.1576 (14)	C4—C5	1.390 (2)
V1—N1	2.2027 (14)	C4—H4	0.9500
V1—O2	2.2934 (12)	C5—C6	1.478 (2)
V1—V1i	3.1165 (6)	C6—C7	1.391 (2)
N1—C1	1.338 (2)	C7—C8	1.388 (3)
N1—C5	1.350 (2)	C7—H7	0.9500
N2—C10	1.341 (2)	C8—C9	1.386 (3)
N2—C6	1.353 (2)	C8—H8	0.9500
C1—C2	1.387 (2)	C9—C10	1.386 (2)
C1—H1	0.9500	C9—H9	0.9500
C2—C3	1.389 (2)	C10—H10	0.9500
O1—V1—O2i	104.55 (6)	N1—C1—H1	118.8
O1—V1—F1	101.51 (6)	C2—C1—H1	118.8
O2i—V1—F1	103.81 (5)	C1—C2—C3	118.95 (16)
O1—V1—N2	91.61 (6)	C1—C2—H2	120.5
O2i—V1—N2	93.00 (5)	C3—C2—H2	120.5
F1—V1—N2	155.14 (5)	C4—C3—C2	118.86 (16)
O1—V1—N1	97.47 (6)	C4—C3—H3	120.6
O2i—V1—N1	154.20 (5)	C2—C3—H3	120.6
F1—V1—N1	84.45 (5)	C3—C4—C5	119.03 (16)
N2—V1—N1	72.87 (5)	C3—C4—H4	120.5
O1—V1—O2	172.25 (6)	C5—C4—H4	120.5
O2i—V1—O2	78.60 (5)	N1—C5—C4	121.90 (16)
F1—V1—O2	84.39 (5)	N1—C5—C6	114.17 (14)
N2—V1—O2	81.09 (5)	C4—C5—C6	123.93 (15)
N1—V1—O2	77.95 (5)	N2—C6—C7	121.90 (16)
O1—V1—V1i	150.07 (5)	N2—C6—C5	114.31 (14)
O2i—V1—V1i	46.17 (4)	C7—C6—C5	123.74 (15)
F1—V1—V1i	93.36 (4)	C8—C7—C6	118.69 (16)
N2—V1—V1i	85.11 (4)	C8—C7—H7	120.7
N1—V1—V1i	109.81 (4)	C6—C7—H7	120.7
O2—V1—V1i	32.44 (3)	C9—C8—C7	119.33 (16)
V1i—O2—V1	101.40 (5)	C9—C8—H8	120.3
C1—N1—C5	118.83 (15)	C7—C8—H8	120.3
C1—N1—V1	122.59 (11)	C10—C9—C8	118.90 (17)
C5—N1—V1	118.50 (11)	C10—C9—H9	120.5
C10—N2—C6	118.87 (15)	C8—C9—H9	120.5
C10—N2—V1	121.00 (11)	N2—C10—C9	122.31 (16)
C6—N2—V1	119.98 (11)	N2—C10—H10	118.8
N1—C1—C2	122.42 (16)	C9—C10—H10	118.8
O2i—V1—O2—V1i	0.0	V1i—V1—N2—C6	−112.39 (12)
F1—V1—O2—V1i	105.34 (6)	C5—N1—C1—C2	−1.6 (3)
N2—V1—O2—V1i	−94.91 (6)	V1—N1—C1—C2	175.09 (13)
N1—V1—O2—V1i	−169.16 (6)	N1—C1—C2—C3	1.0 (3)
O1—V1—N1—C1	91.27 (14)	C1—C2—C3—C4	0.3 (3)
O2i—V1—N1—C1	−120.14 (16)	C2—C3—C4—C5	−1.0 (3)
F1—V1—N1—C1	−9.65 (13)	C1—N1—C5—C4	0.9 (2)
N2—V1—N1—C1	−179.35 (14)	V1—N1—C5—C4	−175.93 (12)
O2—V1—N1—C1	−95.08 (13)	C1—N1—C5—C6	−178.60 (14)
V1i—V1—N1—C1	−101.23 (13)	V1—N1—C5—C6	4.58 (18)
O1—V1—N1—C5	−92.04 (13)	C3—C4—C5—N1	0.4 (3)
O2i—V1—N1—C5	56.55 (19)	C3—C4—C5—C6	179.83 (15)
F1—V1—N1—C5	167.04 (12)	C10—N2—C6—C7	0.1 (2)
N2—V1—N1—C5	−2.66 (11)	V1—N2—C6—C7	−175.39 (12)
O2—V1—N1—C5	81.61 (12)	C10—N2—C6—C5	177.71 (14)
V1i—V1—N1—C5	75.46 (12)	V1—N2—C6—C5	2.18 (18)
O1—V1—N2—C10	−78.03 (14)	N1—C5—C6—N2	−4.3 (2)
O2i—V1—N2—C10	26.64 (13)	C4—C5—C6—N2	176.19 (15)
F1—V1—N2—C10	159.61 (13)	N1—C5—C6—C7	173.19 (15)
N1—V1—N2—C10	−175.34 (14)	C4—C5—C6—C7	−6.3 (3)
O2—V1—N2—C10	104.61 (13)	N2—C6—C7—C8	0.3 (3)
V1i—V1—N2—C10	72.17 (13)	C5—C6—C7—C8	−177.03 (15)
O1—V1—N2—C6	97.41 (13)	C6—C7—C8—C9	−0.2 (3)
O2i—V1—N2—C6	−157.93 (12)	C7—C8—C9—C10	−0.3 (3)
F1—V1—N2—C6	−25.0 (2)	C6—N2—C10—C9	−0.7 (3)
N1—V1—N2—C6	0.09 (12)	V1—N2—C10—C9	174.79 (13)
O2—V1—N2—C6	−79.96 (12)	C8—C9—C10—N2	0.8 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···F1ii	0.95	2.59	3.493 (2)	160.
C2—H2···O1iii	0.95	2.42	3.161 (2)	134.
C3—H3···F1iv	0.95	2.43	3.050 (2)	123.
C3—H3···F1iii	0.95	2.86	3.760 (2)	159.
C4—H4···O2v	0.95	2.52	3.407 (2)	155.
C4—H4···F1iv	0.95	2.60	3.131 (2)	116.
C7—H7···O2v	0.95	2.53	3.366 (2)	147.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯F1i	0.95	2.59	3.493 (2)	160
C2—H2⋯O1ii	0.95	2.42	3.161 (2)	134
C3—H3⋯F1iii	0.95	2.43	3.050 (2)	123
C3—H3⋯F1ii	0.95	2.86	3.760 (2)	159
C4—H4⋯O2iv	0.95	2.52	3.407 (2)	155
C4—H4⋯F1iii	0.95	2.60	3.131 (2)	116
C7—H7⋯O2iv	0.95	2.53	3.366 (2)	147

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