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

The title compound, [V₂F₂O₄(C₁₂H₈N₂)₂], is a centrosymmetric binuclear vanadium(V) species with the metal ions in a distorted octa­hedral 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 inter­molecular C—H...O and C—H...F hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 90 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.034
• wR factor = 0.084
• Data-to-parameter ratio = 15.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X)  V1     --  O1      ..       7.01 su
PLAT912_ALERT_4_C Missing # of FCF Reflections Above STh/L=  0.600         28

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Metal oxyfluorides exhibit a range of compositions and considerable structural versatility that give rise to useful physical properties and potential applications (Adil, et al., 2010; Burkholder & Zubieta, 2004; DeBurgomaster & Zubieta, 2010; Jones et al., 2010; Michailovski, et al., 2006,2009; Ouellette et al., 2005,2006,2007); Ouellette & Zubieta, 2007). Hydrothermal chemistry offers one approach to the preparation of novel metal oxyfluorides where the complexity of the synthetic domain allows incorporation of fluoride into metal oxide frameworks, providing unusual and often unprecedented structures (Gopalakrishnan, 1995; Whittingham, 1996; Zubieta, 2003) Furthermore, the metal-oxyfluoride core can be stabilized or modified by the introduction of appropriate coligands, such as organonitrogen donors of the pyridyl family. In the course of our investigations of the hydrothermal chemistry of metal oxides in the presence of fluoride anion, the title compound [V₂F₂O₄(phen)₂] was isolated. The compound crystallizes in the triclinic space group P1 with one binuclear molecule per unit cell, whose halves are related by a center of symmetry at the mid-point of the V···V vector. The V atoms exhibit distorted octahedral geometry with {VFO₃N₂} coordination (Fig. 1). The µ-bis-oxo bridging mode is characterized by a {V₂O₂} rhombus with alternating short-long V—O bond distances of 1.724 (1) Å and 2.316 (1) Å, respectively. The terminal oxo-groups lie in the plane of the {V₂O₂} rhombus and exhibit a pronounced trans-influence as shown by the elongated bridging oxo-group-vanadium distance, V1—O1. The coordination geometry at the vanadium sites also exhibits a fluoride ligand with V—F of 1.787 (1) Å with the V—F vector approximately normal to the {V₂O₂} rhombus. The V—F vectors of the binuclear unit adopt an anti-orientation with respect to the plane if the {V₂O₂} rhombus. The geometry is completed by the nitrogen donors of the phenanthroline ligand, which occupy positions trans to the short V—O bond of the rhombus and trans to the terminal fluoride ligand. The crystal packing is stabilized by weak intermolecular C—H···O and C—H···F hydrogen bonds which produces two-dimensional connectivity in the bc plane (Figure 2).

Related literature

For the properties and applications of oxyfluoromolybdates and oxyfluorovanadates, 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).

S2. Experimental

A mixture of V₂O₅ (0.062 g, 0.34 mmol), 1,10-phenanthroline (0.367 g, 2.04 mmol), H₂O (5 ml, 277.5 mmol) and HF (0.200 ml, 5.80 mmol) in the mole ratio 1.00:6.03:1620:17.06 was stirred briefly before heating to 170 oC for 48 h (initial and final pH values of 2.5 and 2.0, respectively). Yellow rods suitable for X-ray diffraction were isolated in 65% yield. Anal. Calcd. for C₂₄H₂₀F₂N₄O₄V₂: C, 51.0; H, 2.84; N, 9.92; F, 6.73. Found: C, 50.7;H,3.01;N, 9.67; F, 6.55.

S3. Refinement

All hydrogen atoms were discernable in the difference Fourier map. The hydrogen atoms were placed in calculated positions with C—H = 0.95 Å and included in the riding model approximation with U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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).

Figures

	Fig. 1. View of the molecular dimer of the title compound, with the atom-labeling scheme and the displacement ellipsoids drawn at the 50% probability level. Color scheme: vanadium, orange; oxygen, red; fluorine, green; nitrogen, light blue; carbon, black; hydrogen, pink.
	Fig. 2. A packing diagram illustrating the C-H···O and C-H···F contacts (illustrated as multiband cylinders). Color code as for Fig. 1.

di-µ-oxido-bis[fluoridooxido(1,10-phenanthroline)vanadium(V)]

Crystal data

[V2F2O4(C12H8N2)2]	Z = 1
Mr = 564.29	F(000) = 284.0
Triclinic, P1	Dx = 1.773 Mg m^−3 Dm = 1.77 (2) Mg m^−3 Dm 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) Å^3

Data collection

Bruker APEX CCD diffractometer	2550 independent reflections
Radiation source: fine-focus sealed tube	2502 reflections with I > 2σ(I)
Graphite monochromator	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

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.084	H-atom parameters constrained
S = 1.14	w = 1/[σ^2(Fo^2) + (0.0297P)^2 + 0.608P] where P = (Fo^2 + 2Fc^2)/3
2550 reflections	(Δ/σ)max = 0.001
163 parameters	Δρmax = 0.41 e Å^−3
0 restraints	Δρmin = −0.35 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
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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—O1^i	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—O1^i	170.39 (6)	C4—C6—H6	119.6
O1—V1—O1^i	76.95 (6)	C6—C7—C8	121.25 (17)
F1—V1—O1^i	86.10 (5)	C6—C7—H7	119.4
N2—V1—O1^i	78.88 (5)	C8—C7—H7	119.4
N1—V1—O1^i	77.68 (5)	C9—C8—C10	117.11 (17)
V1—O1—V1^i	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—V1^i	−170.30 (6)	C1—N1—C5—C4	1.1 (3)
F1—V1—O1—V1^i	82.35 (6)	V1—N1—C5—C4	178.74 (13)
N2—V1—O1—V1^i	−78.46 (6)	C1—N1—C5—C9	−179.58 (16)
N1—V1—O1—V1^i	−24.09 (15)	V1—N1—C5—C9	−1.9 (2)
O1^i—V1—O1—V1^i	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)
O1^i—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)
O1^i—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)
O1^i—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)
O1^i—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)

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···F1^ii	0.95	2.49	3.393 (2)	160
C3—H3···O1^iii	0.95	2.44	3.191 (2)	136
C6—H6···O1^iii	0.95	2.46	3.200 (2)	135
C10—H10···O2^iv	0.95	2.39	3.282 (2)	157

Symmetry codes: (ii) −x+1, −y+1, −z+1; (iii) x, y, z−1; (iv) x, y+1, z.