A binuclear vanadium oxyfluoride: di-μ-oxido-bis-[fluoridooxido(1,10-phenanthro-line)vanadium(V)].

The title compound, [V(2)F(2)O(4)(C(12)H(8)N(2))(2)], is a centrosymmetric binuclear vanadium(V) species with the metal ions in a distorted octa-hedral environment. The symmetry-equivalent V(V) atoms exhibit coordination geometries defined by cis-terminal fluoride and oxide groups, unsymmetrically bridging oxide groups and the N-atom donors of the phenanthroline ligands. The crystal packing is stabilized by weak inter-molecular C-H⋯O and C-H⋯F hydrogen bonds.

Related literature

For the properties and applications of oxyfluorido­molybdates and -­vanadates, see: Adil et al. (2010 ▶); Burkholder & Zubieta (2004 ▶); DeBurgomaster & Zubieta (2010 ▶); Jones et al. (2010 ▶); Michailovski et al. (2006 ▶, 2009 ▶). For examples of solid phase vanadium oxyfluorides in the presence of coligands, see: Ouellette et al. (2005 ▶, 2006 ▶, 2007 ▶); Ouellette & Zubieta (2007 ▶). For hydro­thermal preparation of metal oxyfluorides, see: Gopalakrishnan (1995 ▶); Whittingham (1996 ▶); Zubieta (2003 ▶).

Experimental

Crystal data

[V2F2O4(C12H8N2)2]

M = 564.29

Triclinic,

a = 7.8320 (9) Å

b = 8.4937 (10) Å

c = 9.2007 (11) Å

α = 113.741 (3)°

β = 102.834 (2)°

γ = 97.848 (2)°

V = 528.46 (11) Å3

Z = 1

Mo Kα radiation

μ = 0.95 mm−1

T = 90 K

0.36 × 0.31 × 0.12 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.626, T max = 0.747

5297 measured reflections

2550 independent reflections

2502 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.084

S = 1.14

2550 reflections

163 parameters

H-atom parameters constrained

Δρmax = 0.41 e Å−3

Δρmin = −0.35 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/S1600536810037232/lh5133sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810037232/lh5133Isup2.hkl

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

[V2F2O4(C12H8N2)2]	Z = 1
Mr = 564.29	F(000) = 284.0
Triclinic, P1	Dx = 1.773 Mg m−3Dm = 1.77 (2) Mg m−3Dm measured by flotation
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8320 (9) Å	Cell parameters from 3266 reflections
b = 8.4937 (10) Å	θ = 2.4–28.3°
c = 9.2007 (11) Å	µ = 0.95 mm−1
α = 113.741 (3)°	T = 90 K
β = 102.834 (2)°	Plate, yellow
γ = 97.848 (2)°	0.36 × 0.31 × 0.12 mm
V = 528.46 (11) Å3

Bruker APEX CCD diffractometer	2550 independent reflections
Radiation source: fine-focus sealed tube	2502 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 = −10→9
Absorption correction: multi-scan (SADABS; Bruker, 1998)	k = −11→11
Tmin = 0.626, Tmax = 0.747	l = −12→12
5297 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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H-atom parameters constrained
S = 1.14	w = 1/[σ2(Fo2) + (0.0297P)2 + 0.608P] where P = (Fo2 + 2Fc2)/3
2550 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.41 e Å−3
0 restraints	Δρmin = −0.35 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	0.32341 (4)	0.84898 (4)	0.86984 (4)	0.01413 (10)
F1	0.43262 (16)	0.67119 (15)	0.83110 (14)	0.0199 (2)
O1	0.39833 (17)	0.97396 (17)	1.08350 (15)	0.0130 (3)
O2	0.11464 (19)	0.74797 (18)	0.82733 (18)	0.0182 (3)
N1	0.3194 (2)	0.8039 (2)	0.61559 (19)	0.0128 (3)
N2	0.2439 (2)	1.0719 (2)	0.83968 (19)	0.0131 (3)
C1	0.3604 (2)	0.6671 (2)	0.5064 (2)	0.0152 (4)
H1	0.3896	0.5771	0.5364	0.018*
C2	0.3623 (3)	0.6503 (3)	0.3487 (2)	0.0168 (4)
H2	0.3938	0.5514	0.2746	0.020*
C3	0.3182 (2)	0.7782 (3)	0.3023 (2)	0.0161 (4)
H3	0.3184	0.7682	0.1957	0.019*
C4	0.2724 (2)	0.9249 (2)	0.4151 (2)	0.0143 (3)
C5	0.2775 (2)	0.9315 (2)	0.5709 (2)	0.0121 (3)
C6	0.2197 (2)	1.0641 (3)	0.3789 (2)	0.0169 (4)
H6	0.2146	1.0606	0.2735	0.020*
C7	0.1770 (2)	1.2007 (3)	0.4937 (2)	0.0167 (4)
H7	0.1410	1.2904	0.4666	0.020*
C8	0.1852 (2)	1.2119 (2)	0.6554 (2)	0.0144 (3)
C9	0.2355 (2)	1.0768 (2)	0.6925 (2)	0.0126 (3)
C10	0.1417 (2)	1.3488 (2)	0.7797 (2)	0.0168 (4)
H10	0.1096	1.4451	0.7621	0.020*
C11	0.1464 (3)	1.3406 (3)	0.9264 (2)	0.0180 (4)
H11	0.1145	1.4302	1.0103	0.022*
C12	0.1982 (3)	1.2007 (2)	0.9531 (2)	0.0159 (4)
H12	0.2008	1.1976	1.0556	0.019*

	U11	U22	U33	U12	U13	U23
V1	0.01424 (17)	0.01694 (17)	0.01513 (17)	0.00489 (12)	0.00478 (12)	0.01048 (13)
F1	0.0238 (6)	0.0184 (5)	0.0203 (6)	0.0093 (5)	0.0074 (5)	0.0096 (5)
O1	0.0156 (6)	0.0145 (6)	0.0113 (6)	0.0054 (5)	0.0052 (5)	0.0070 (5)
O2	0.0174 (7)	0.0177 (6)	0.0218 (7)	0.0049 (5)	0.0070 (5)	0.0103 (6)
N1	0.0115 (7)	0.0145 (7)	0.0125 (7)	0.0039 (6)	0.0032 (6)	0.0060 (6)
N2	0.0123 (7)	0.0144 (7)	0.0120 (7)	0.0044 (6)	0.0033 (6)	0.0054 (6)
C1	0.0142 (8)	0.0153 (8)	0.0155 (9)	0.0053 (7)	0.0042 (7)	0.0059 (7)
C2	0.0153 (9)	0.0181 (9)	0.0121 (8)	0.0032 (7)	0.0049 (7)	0.0021 (7)
C3	0.0136 (8)	0.0210 (9)	0.0115 (8)	0.0022 (7)	0.0043 (7)	0.0059 (7)
C4	0.0100 (8)	0.0177 (8)	0.0139 (8)	0.0009 (6)	0.0023 (6)	0.0075 (7)
C5	0.0097 (8)	0.0137 (8)	0.0129 (8)	0.0028 (6)	0.0028 (6)	0.0064 (7)
C6	0.0129 (8)	0.0230 (9)	0.0171 (9)	0.0011 (7)	0.0024 (7)	0.0134 (8)
C7	0.0136 (8)	0.0182 (9)	0.0213 (9)	0.0024 (7)	0.0030 (7)	0.0134 (8)
C8	0.0098 (8)	0.0151 (8)	0.0176 (9)	0.0018 (6)	0.0017 (7)	0.0083 (7)
C9	0.0099 (8)	0.0137 (8)	0.0136 (8)	0.0025 (6)	0.0026 (6)	0.0061 (7)
C10	0.0123 (8)	0.0131 (8)	0.0231 (10)	0.0035 (7)	0.0015 (7)	0.0081 (7)
C11	0.0162 (9)	0.0154 (9)	0.0174 (9)	0.0067 (7)	0.0023 (7)	0.0031 (7)
C12	0.0159 (9)	0.0168 (8)	0.0132 (8)	0.0061 (7)	0.0038 (7)	0.0046 (7)

V1—O2	1.6203 (14)	C3—H3	0.9500
V1—O1	1.7241 (13)	C4—C5	1.404 (2)
V1—F1	1.7871 (12)	C4—C6	1.438 (3)
V1—N2	2.1724 (16)	C5—C9	1.430 (2)
V1—N1	2.2052 (16)	C6—C7	1.360 (3)
V1—O1i	2.3162 (13)	C6—H6	0.9500
N1—C1	1.330 (2)	C7—C8	1.438 (3)
N1—C5	1.358 (2)	C7—H7	0.9500
N2—C12	1.329 (2)	C8—C9	1.402 (2)
N2—C9	1.359 (2)	C8—C10	1.409 (3)
C1—C2	1.403 (3)	C10—C11	1.373 (3)
C1—H1	0.9500	C10—H10	0.9500
C2—C3	1.376 (3)	C11—C12	1.400 (3)
C2—H2	0.9500	C11—H11	0.9500
C3—C4	1.415 (3)	C12—H12	0.9500
O2—V1—O1	104.98 (7)	C2—C3—H3	120.4
O2—V1—F1	102.29 (6)	C4—C3—H3	120.4
O1—V1—F1	104.75 (6)	C5—C4—C3	116.98 (17)
O2—V1—N2	91.64 (6)	C5—C4—C6	118.79 (17)
O1—V1—N2	90.52 (6)	C3—C4—C6	124.22 (17)
F1—V1—N2	155.64 (6)	N1—C5—C4	123.54 (17)
O2—V1—N1	98.29 (6)	N1—C5—C9	116.19 (16)
O1—V1—N1	152.31 (6)	C4—C5—C9	120.27 (16)
F1—V1—N1	84.36 (6)	C7—C6—C4	120.81 (17)
N2—V1—N1	73.81 (6)	C7—C6—H6	119.6
O2—V1—O1i	170.39 (6)	C4—C6—H6	119.6
O1—V1—O1i	76.95 (6)	C6—C7—C8	121.25 (17)
F1—V1—O1i	86.10 (5)	C6—C7—H7	119.4
N2—V1—O1i	78.88 (5)	C8—C7—H7	119.4
N1—V1—O1i	77.68 (5)	C9—C8—C10	117.11 (17)
V1—O1—V1i	103.05 (6)	C9—C8—C7	118.67 (17)
C1—N1—C5	118.04 (16)	C10—C8—C7	124.21 (17)
C1—N1—V1	125.58 (12)	N2—C9—C8	123.62 (17)
C5—N1—V1	116.33 (12)	N2—C9—C5	116.17 (16)
C12—N2—C9	117.95 (16)	C8—C9—C5	120.20 (17)
C12—N2—V1	124.57 (13)	C11—C10—C8	118.87 (17)
C9—N2—V1	117.45 (12)	C11—C10—H10	120.6
N1—C1—C2	122.64 (17)	C8—C10—H10	120.6
N1—C1—H1	118.7	C10—C11—C12	120.26 (18)
C2—C1—H1	118.7	C10—C11—H11	119.9
C3—C2—C1	119.50 (17)	C12—C11—H11	119.9
C3—C2—H2	120.2	N2—C12—C11	122.16 (18)
C1—C2—H2	120.2	N2—C12—H12	118.9
C2—C3—C4	119.27 (17)	C11—C12—H12	118.9
O2—V1—O1—V1i	−170.30 (6)	C1—N1—C5—C4	1.1 (3)
F1—V1—O1—V1i	82.35 (6)	V1—N1—C5—C4	178.74 (13)
N2—V1—O1—V1i	−78.46 (6)	C1—N1—C5—C9	−179.58 (16)
N1—V1—O1—V1i	−24.09 (15)	V1—N1—C5—C9	−1.9 (2)
O1i—V1—O1—V1i	0.0	C3—C4—C5—N1	−1.6 (3)
O2—V1—N1—C1	−91.43 (15)	C6—C4—C5—N1	177.65 (16)
O1—V1—N1—C1	121.45 (17)	C3—C4—C5—C9	179.14 (16)
F1—V1—N1—C1	10.21 (15)	C6—C4—C5—C9	−1.7 (3)
N2—V1—N1—C1	179.27 (16)	C5—C4—C6—C7	0.6 (3)
O1i—V1—N1—C1	97.44 (15)	C3—C4—C6—C7	179.75 (17)
O2—V1—N1—C5	91.11 (13)	C4—C6—C7—C8	0.8 (3)
O1—V1—N1—C5	−56.00 (19)	C6—C7—C8—C9	−1.1 (3)
F1—V1—N1—C5	−167.25 (13)	C6—C7—C8—C10	−179.54 (18)
N2—V1—N1—C5	1.81 (12)	C12—N2—C9—C8	1.4 (3)
O1i—V1—N1—C5	−80.02 (12)	V1—N2—C9—C8	179.58 (13)
O2—V1—N2—C12	78.41 (16)	C12—N2—C9—C5	−177.17 (16)
O1—V1—N2—C12	−26.60 (15)	V1—N2—C9—C5	1.0 (2)
F1—V1—N2—C12	−156.19 (15)	C10—C8—C9—N2	0.1 (3)
N1—V1—N2—C12	176.56 (16)	C7—C8—C9—N2	−178.51 (16)
O1i—V1—N2—C12	−103.19 (15)	C10—C8—C9—C5	178.59 (16)
O2—V1—N2—C9	−99.64 (13)	C7—C8—C9—C5	0.0 (3)
O1—V1—N2—C9	155.36 (13)	N1—C5—C9—N2	0.6 (2)
F1—V1—N2—C9	25.8 (2)	C4—C5—C9—N2	179.98 (16)
N1—V1—N2—C9	−1.48 (12)	N1—C5—C9—C8	−178.00 (16)
O1i—V1—N2—C9	78.77 (13)	C4—C5—C9—C8	1.4 (3)
C5—N1—C1—C2	0.1 (3)	C9—C8—C10—C11	−1.6 (3)
V1—N1—C1—C2	−177.28 (13)	C7—C8—C10—C11	176.93 (17)
N1—C1—C2—C3	−0.8 (3)	C8—C10—C11—C12	1.6 (3)
C1—C2—C3—C4	0.3 (3)	C9—N2—C12—C11	−1.4 (3)
C2—C3—C4—C5	0.8 (3)	V1—N2—C12—C11	−179.42 (14)
C2—C3—C4—C6	−178.35 (17)	C10—C11—C12—N2	−0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F1ii	0.95	2.49	3.393 (2)	160
C3—H3···O1iii	0.95	2.44	3.191 (2)	136
C6—H6···O1iii	0.95	2.46	3.200 (2)	135
C10—H10···O2iv	0.95	2.39	3.282 (2)	157

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯F1i	0.95	2.49	3.393 (2)	160
C3—H3⋯O1ii	0.95	2.44	3.191 (2)	136
C6—H6⋯O1ii	0.95	2.46	3.200 (2)	135
C10—H10⋯O2iii	0.95	2.39	3.282 (2)	157

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