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Acta Cryst. (2009). E65, m1114    [ doi:10.1107/S1600536809032516 ]

Di-[mu]-oxido-bis[(4-formyl-2-methoxyphenolato-[kappa]O1)oxido(1,10-phenanthroline-[kappa]2N,N')vanadium(V)]

Z. Guo, L. Li, T. Xu and J. Li

Abstract top

The title complex, [V2(C8H7O3)2O4(C12H8N2)2], is a centrosymmetric dimer formed by two VV complex units bridged by two [mu]2-oxido groups. The VV atom is six-coordinated by three oxide O atoms, one O atom from a vanillinate ligand and two N atoms from a 1,10-phenanthroline ligand in a significantly distorted octahedral geometry. In the crystal structure, weak intermolecular C-H...O hydrogen bonds connect the molecules into a three-dimensional network.

Comment top

There is an increased interest in vanadium complexes due to their possible uses in pharmaceuticals for the treatment of diabetes (Thompson et al., 1999) and their practical applications in catalysis and material science (Yuan et al., 2003). The vanadium complexes with 1,10-phenanthroline ligand have been reported to exhibit potent antitumor activity (Dong et al., 2000). Vanillin is an useful organic compound with multifunctional groups including aldehyde, ether and phenol. In an effort to uncover the chemistry and biochemistry of vanadium with nitrogen- and oxygen-containing ligands, we report herein the synthesis and crystal structure of a new binuclear vanadium(V) complexes with mixed ligands of vanillin and 1,10-phenanthroline.

The molecular structure of the title complex is shown in Fig.1. In the presence of atmosphere, VIV is oxidized to VV. The complex is centrosymmetric dimer formed by two VV complex untis bridged by two µ2-oxido groups. The VV atom is six-coordinated by three oxido O atoms, one O atom from a vanillinate ligand and two N atoms from a 1,10-phenanthroline ligand in a significantly distorted octahedral geometry (Table 1). O3, O4, N1 and N2 are situated in the equatorial plane and O5 and O4i [symmetry code: (i) -x+2, -y+2, -z+1] are in the axial positions. The VV atom deviates from the least-squares plane of O3, O4, N1 and N2 by 0.319 (1) Å. In the complex, V1—O4 is 1.657 (3) Å and V1—O4i is 2.346 (3) Å, which illustrates that it is a very asymmetric bridge. The asymmetric structure is similar to that previously reported (Li et al., 2004; Mokry & Carrano, 1993).

There are extensive C—H···O hydrogen bonds in the crystal structure (Table 2). As shown in Fig. 2, the neighboring binuclear complex molecules are connected by the intermolecular hydrogen bonds into a three-dimensional network.

Related literature top

For general background to vanadium complexes, see: Dong et al. (2000); Thompson et al. (1999); Yuan et al. (2003). For related structures, see: Li et al. (2004); Mokry & Carrano (1993).

Experimental top

Vanillin (0.152 g, 1 mmol) was dissolved in 5 ml absolute methanol and vanadyl sulfate hydrate (0.225 g, 1 mmol) was added to the solution, which was stirred and refluxed for 2 h at 323 K. Then, a methanol solution (5 ml) of 1,10-phenanthroline (0.198 g, 1 mmol) was added to the solution. The mixture was stirred and refluxed for 3 h at 323 K. The obtained brown solution was cooled to room temperature and filtered. The filtrate was kept at room temperature for 30 d. The crystals suitable for X-ray diffraction were obtained.

Refinement top

H atoms were placed in geometrically calculated positions and allowed to ride on their parent atoms, with C—H = 0.93 (CH) and 0.96 (CH3) Å and with Uiso(H) = 1.2(or 1.5 for methyl)Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 30% probability displacement ellipsoids. [Symmetry code: (i) -x+2, -y+2, -z+1.]
[Figure 2] Fig. 2. The crystal packing of the title compound with hydrogen bonds (dashed lines).
Di-µ-oxido-bis[(4-formyl-2-methoxyphenolato-κO1)oxido(1,10- phenanthroline-κ2N,N')vanadium(V)] top
Crystal data top
[V2(C8H7O3)2O4(C12H8N2)2]Z = 1
Mr = 828.56F(000) = 424
Triclinic, P1Dx = 1.571 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 9.3453 (18) ÅCell parameters from 943 reflections
b = 9.786 (2) Åθ = 2.5–25.8°
c = 11.090 (3) ŵ = 0.60 mm−1
α = 80.097 (2)°T = 298 K
β = 65.672 (1)°Needle, colorless
γ = 71.535 (1)°0.21 × 0.18 × 0.17 mm
V = 875.6 (3) Å3
Data collection top
Bruker SMART 1000 CCD
diffractometer		3038 independent reflections
Radiation source: fine-focus sealed tube2372 reflections with I > 2σ(I)
graphiteRint = 0.046
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→11
Tmin = 0.884, Tmax = 0.904k = −11→8
4641 measured reflectionsl = −13→12
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.061Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177H-atom parameters constrained
S = 1.07 w = 1/[σ2(Fo2) + (0.1054P)2 + 0.2207P]
where P = (Fo2 + 2Fc2)/3
3038 reflections(Δ/σ)max < 0.001
254 parametersΔρmax = 0.84 e Å−3
0 restraintsΔρmin = −0.81 e Å−3
Crystal data top
[V2(C8H7O3)2O4(C12H8N2)2]γ = 71.535 (1)°
Mr = 828.56V = 875.6 (3) Å3
Triclinic, P1Z = 1
a = 9.3453 (18) ÅMo Kα radiation
b = 9.786 (2) ŵ = 0.60 mm−1
c = 11.090 (3) ÅT = 298 K
α = 80.097 (2)°0.21 × 0.18 × 0.17 mm
β = 65.672 (1)°
Data collection top
Bruker SMART 1000 CCD
diffractometer		3038 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2372 reflections with I > 2σ(I)
Tmin = 0.884, Tmax = 0.904Rint = 0.046
4641 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.061H-atom parameters constrained
wR(F2) = 0.177Δρmax = 0.84 e Å−3
S = 1.07Δρmin = −0.81 e Å−3
3038 reflectionsAbsolute structure: ?
254 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
V10.93548 (8)0.89398 (7)0.61983 (7)0.0324 (3)
N11.0193 (4)0.7386 (3)0.4733 (3)0.0337 (7)
N20.7109 (4)0.8658 (3)0.6109 (3)0.0329 (7)
O10.6378 (5)1.4243 (4)1.1968 (4)0.0683 (10)
O20.4949 (4)1.1848 (4)0.8894 (3)0.0544 (9)
O30.7773 (3)1.0430 (3)0.7319 (3)0.0385 (7)
O41.1051 (3)0.9466 (3)0.5544 (3)0.0340 (6)
O50.9616 (4)0.7689 (3)0.7300 (3)0.0439 (7)
C10.7557 (7)1.3424 (6)1.1248 (5)0.0544 (12)
H10.85441.33121.13210.065*
C20.7590 (6)1.2582 (5)1.0265 (5)0.0448 (11)
C30.6170 (5)1.2648 (5)1.0102 (4)0.0434 (10)
H30.51681.32121.06430.052*
C40.6250 (5)1.1877 (5)0.9139 (4)0.0366 (9)
C50.7772 (5)1.1044 (4)0.8284 (4)0.0350 (9)
C60.9175 (5)1.0962 (5)0.8477 (5)0.0435 (10)
H61.01821.03990.79420.052*
C70.9070 (6)1.1723 (5)0.9469 (5)0.0465 (11)
H71.00111.16540.96010.056*
C80.3380 (6)1.2439 (6)0.9822 (6)0.0684 (16)
H8A0.32891.19971.06840.103*
H8B0.25821.22640.95780.103*
H8C0.31951.34590.98400.103*
C91.1750 (5)0.6719 (4)0.4093 (4)0.0379 (9)
H91.25350.69510.42690.046*
C101.2269 (5)0.5683 (4)0.3167 (4)0.0423 (10)
H101.33730.52320.27420.051*
C111.1117 (6)0.5345 (4)0.2897 (4)0.0448 (11)
H111.14380.46560.22870.054*
C120.9468 (5)0.6033 (4)0.3537 (4)0.0398 (10)
C130.9066 (5)0.7047 (4)0.4456 (4)0.0301 (8)
C140.7401 (5)0.7743 (4)0.5200 (4)0.0326 (9)
C150.6154 (5)0.7467 (5)0.4962 (5)0.0419 (10)
C160.4555 (5)0.8190 (5)0.5727 (5)0.0503 (12)
H160.36830.80400.56160.060*
C170.4273 (5)0.9118 (5)0.6636 (5)0.0491 (11)
H170.32080.96080.71420.059*
C180.5583 (5)0.9333 (5)0.6811 (4)0.0407 (10)
H180.53750.99670.74370.049*
C190.8183 (6)0.5772 (5)0.3311 (5)0.0510 (12)
H190.84380.51200.26860.061*
C200.6622 (6)0.6447 (5)0.3981 (5)0.0519 (12)
H200.58130.62540.38090.062*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.0238 (4)0.0321 (4)0.0453 (4)−0.0028 (3)−0.0170 (3)−0.0116 (3)
N10.0333 (18)0.0263 (17)0.0485 (19)−0.0051 (14)−0.0234 (15)−0.0047 (14)
N20.0259 (17)0.0315 (18)0.0425 (19)−0.0053 (14)−0.0152 (14)−0.0043 (14)
O10.067 (3)0.074 (3)0.067 (2)−0.010 (2)−0.023 (2)−0.037 (2)
O20.0297 (16)0.074 (2)0.063 (2)−0.0057 (15)−0.0158 (15)−0.0325 (17)
O30.0272 (14)0.0411 (16)0.0473 (17)0.0006 (12)−0.0148 (12)−0.0200 (13)
O40.0232 (13)0.0363 (15)0.0449 (15)−0.0048 (11)−0.0131 (12)−0.0143 (12)
O50.0441 (17)0.0433 (17)0.0491 (17)−0.0068 (14)−0.0247 (14)−0.0059 (14)
C10.061 (3)0.060 (3)0.050 (3)−0.020 (3)−0.025 (3)−0.009 (2)
C20.050 (3)0.042 (3)0.050 (3)−0.012 (2)−0.025 (2)−0.007 (2)
C30.038 (2)0.045 (3)0.044 (2)−0.0042 (19)−0.0143 (19)−0.013 (2)
C40.033 (2)0.040 (2)0.037 (2)−0.0078 (18)−0.0139 (17)−0.0046 (18)
C50.036 (2)0.035 (2)0.033 (2)−0.0100 (18)−0.0114 (17)−0.0038 (17)
C60.035 (2)0.041 (2)0.057 (3)0.0017 (18)−0.025 (2)−0.014 (2)
C70.041 (3)0.051 (3)0.058 (3)−0.010 (2)−0.028 (2)−0.007 (2)
C80.035 (3)0.086 (4)0.079 (4)−0.006 (3)−0.013 (3)−0.033 (3)
C90.030 (2)0.032 (2)0.052 (2)−0.0033 (17)−0.0182 (19)−0.0039 (18)
C100.038 (2)0.031 (2)0.049 (2)0.0012 (18)−0.013 (2)−0.0095 (19)
C110.058 (3)0.030 (2)0.045 (2)−0.007 (2)−0.019 (2)−0.0094 (19)
C120.048 (3)0.030 (2)0.048 (2)−0.0098 (19)−0.026 (2)−0.0034 (18)
C130.030 (2)0.030 (2)0.033 (2)−0.0093 (16)−0.0142 (16)−0.0009 (16)
C140.028 (2)0.030 (2)0.044 (2)−0.0087 (16)−0.0190 (17)0.0004 (17)
C150.040 (2)0.038 (2)0.063 (3)−0.0146 (19)−0.034 (2)0.006 (2)
C160.038 (3)0.052 (3)0.076 (3)−0.018 (2)−0.037 (2)0.005 (2)
C170.027 (2)0.052 (3)0.068 (3)−0.009 (2)−0.020 (2)−0.002 (2)
C180.027 (2)0.040 (2)0.053 (3)−0.0036 (18)−0.0163 (19)−0.004 (2)
C190.060 (3)0.049 (3)0.064 (3)−0.016 (2)−0.037 (3)−0.014 (2)
C200.057 (3)0.051 (3)0.071 (3)−0.020 (2)−0.043 (3)−0.002 (2)
Geometric parameters (Å, °) top
V1—O31.898 (3)C7—H70.9300
V1—O41.657 (3)C8—H8A0.9600
V1—O51.610 (3)C8—H8B0.9600
V1—O4i2.346 (3)C8—H8C0.9600
V1—N12.148 (3)C9—C101.398 (6)
V1—N22.245 (3)C9—H90.9300
N1—C91.324 (5)C10—C111.372 (6)
N1—C131.355 (5)C10—H100.9300
N2—C181.319 (5)C11—C121.392 (6)
N2—C141.350 (5)C11—H110.9300
O1—C11.196 (6)C12—C131.400 (6)
O2—C41.359 (5)C12—C191.426 (6)
O2—C81.403 (6)C13—C141.425 (6)
O3—C51.314 (5)C14—C151.407 (5)
O4—V1i2.346 (3)C15—C161.395 (7)
C1—C21.459 (6)C15—C201.440 (7)
C1—H10.9300C16—C171.362 (7)
C2—C71.383 (7)C16—H160.9300
C2—C31.393 (6)C17—C181.398 (6)
C3—C41.375 (6)C17—H170.9300
C3—H30.9300C18—H180.9300
C4—C51.416 (6)C19—C201.335 (7)
C5—C61.390 (6)C19—H190.9300
C6—C71.385 (6)C20—H200.9300
C6—H60.9300
O5—V1—O4105.63 (14)C6—C7—H7119.4
O5—V1—O399.73 (14)O2—C8—H8A109.5
O4—V1—O3105.13 (13)O2—C8—H8B109.5
O5—V1—N191.67 (14)H8A—C8—H8B109.5
O4—V1—N193.98 (13)O2—C8—H8C109.5
O3—V1—N1154.01 (13)H8A—C8—H8C109.5
O5—V1—N299.66 (13)H8B—C8—H8C109.5
O4—V1—N2152.20 (13)N1—C9—C10123.1 (4)
O3—V1—N281.37 (12)N1—C9—H9118.5
N1—V1—N273.69 (12)C10—C9—H9118.5
O5—V1—O4i172.60 (13)C11—C10—C9118.7 (4)
O4—V1—O4i77.95 (12)C11—C10—H10120.6
O3—V1—O4i85.35 (11)C9—C10—H10120.6
N1—V1—O4i81.55 (11)C10—C11—C12120.0 (4)
N2—V1—O4i75.66 (10)C10—C11—H11120.0
C9—N1—C13117.7 (3)C12—C11—H11120.0
C9—N1—V1123.9 (3)C11—C12—C13117.1 (4)
C13—N1—V1118.3 (3)C11—C12—C19124.3 (4)
C18—N2—C14118.8 (3)C13—C12—C19118.6 (4)
C18—N2—V1126.4 (3)N1—C13—C12123.4 (4)
C14—N2—V1114.8 (2)N1—C13—C14116.2 (3)
C4—O2—C8118.0 (4)C12—C13—C14120.4 (3)
C5—O3—V1132.1 (3)N2—C14—C15123.2 (4)
V1—O4—V1i102.05 (12)N2—C14—C13117.0 (3)
O1—C1—C2126.1 (5)C15—C14—C13119.9 (4)
O1—C1—H1117.0C16—C15—C14116.6 (4)
C2—C1—H1117.0C16—C15—C20125.5 (4)
C7—C2—C3119.6 (4)C14—C15—C20117.9 (4)
C7—C2—C1119.1 (4)C17—C16—C15119.8 (4)
C3—C2—C1121.3 (4)C17—C16—H16120.1
C4—C3—C2119.9 (4)C15—C16—H16120.1
C4—C3—H3120.1C16—C17—C18120.0 (4)
C2—C3—H3120.1C16—C17—H17120.0
O2—C4—C3125.1 (4)C18—C17—H17120.0
O2—C4—C5114.2 (4)N2—C18—C17121.6 (4)
C3—C4—C5120.7 (4)N2—C18—H18119.2
O3—C5—C6123.8 (4)C17—C18—H18119.2
O3—C5—C4117.4 (4)C20—C19—C12121.2 (4)
C6—C5—C4118.8 (4)C20—C19—H19119.4
C7—C6—C5119.8 (4)C12—C19—H19119.4
C7—C6—H6120.1C19—C20—C15121.9 (4)
C5—C6—H6120.1C19—C20—H20119.1
C2—C7—C6121.2 (4)C15—C20—H20119.1
C2—C7—H7119.4
O5—V1—N1—C9−77.6 (3)C3—C4—C5—C63.1 (6)
O4—V1—N1—C928.2 (3)O3—C5—C6—C7175.7 (4)
O3—V1—N1—C9166.0 (3)C4—C5—C6—C7−1.8 (6)
N2—V1—N1—C9−177.1 (3)C3—C2—C7—C62.3 (7)
O4i—V1—N1—C9105.4 (3)C1—C2—C7—C6−176.7 (4)
O5—V1—N1—C13101.4 (3)C5—C6—C7—C2−0.9 (7)
O4—V1—N1—C13−152.8 (3)C13—N1—C9—C10−0.7 (6)
O3—V1—N1—C13−15.1 (5)V1—N1—C9—C10178.3 (3)
N2—V1—N1—C131.8 (3)N1—C9—C10—C110.5 (6)
O4i—V1—N1—C13−75.6 (3)C9—C10—C11—C120.2 (6)
O5—V1—N2—C1891.8 (3)C10—C11—C12—C13−0.7 (6)
O4—V1—N2—C18−112.8 (4)C10—C11—C12—C19179.1 (4)
O3—V1—N2—C18−6.6 (3)C9—N1—C13—C120.1 (6)
N1—V1—N2—C18−179.2 (4)V1—N1—C13—C12−178.9 (3)
O4i—V1—N2—C18−94.0 (3)C9—N1—C13—C14177.6 (3)
O5—V1—N2—C14−90.9 (3)V1—N1—C13—C14−1.4 (4)
O4—V1—N2—C1464.4 (4)C11—C12—C13—N10.5 (6)
O3—V1—N2—C14170.6 (3)C19—C12—C13—N1−179.2 (4)
N1—V1—N2—C14−2.0 (3)C11—C12—C13—C14−176.8 (4)
O4i—V1—N2—C1483.2 (3)C19—C12—C13—C143.4 (6)
O5—V1—O3—C555.9 (3)C18—N2—C14—C15−0.1 (6)
O4—V1—O3—C5−53.3 (3)V1—N2—C14—C15−177.6 (3)
N1—V1—O3—C5170.7 (3)C18—N2—C14—C13179.5 (3)
N2—V1—O3—C5154.3 (3)V1—N2—C14—C132.0 (4)
O4i—V1—O3—C5−129.5 (3)N1—C13—C14—N2−0.5 (5)
O5—V1—O4—V1i173.33 (13)C12—C13—C14—N2177.1 (3)
O3—V1—O4—V1i−81.74 (13)N1—C13—C14—C15179.1 (3)
N1—V1—O4—V1i80.47 (12)C12—C13—C14—C15−3.3 (6)
N2—V1—O4—V1i18.6 (3)N2—C14—C15—C16−0.3 (6)
O4i—V1—O4—V1i0.0C13—C14—C15—C16−179.9 (4)
O1—C1—C2—C7177.4 (5)N2—C14—C15—C20−178.9 (4)
O1—C1—C2—C3−1.6 (8)C13—C14—C15—C201.5 (6)
C7—C2—C3—C4−1.0 (7)C14—C15—C16—C170.6 (6)
C1—C2—C3—C4178.0 (4)C20—C15—C16—C17179.2 (4)
C8—O2—C4—C3−11.6 (7)C15—C16—C17—C18−0.6 (7)
C8—O2—C4—C5169.6 (4)C14—N2—C18—C170.2 (6)
C2—C3—C4—O2179.5 (4)V1—N2—C18—C17177.3 (3)
C2—C3—C4—C5−1.7 (6)C16—C17—C18—N20.2 (7)
V1—O3—C5—C617.7 (6)C11—C12—C19—C20178.5 (4)
V1—O3—C5—C4−164.7 (3)C13—C12—C19—C20−1.7 (7)
O2—C4—C5—O34.3 (5)C12—C19—C20—C15−0.1 (8)
C3—C4—C5—O3−174.6 (3)C16—C15—C20—C19−178.3 (5)
O2—C4—C5—C6−178.0 (4)C14—C15—C20—C190.2 (7)
Symmetry codes: (i) −x+2, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O1ii0.932.483.393 (6)168
C16—H16···O4iii0.932.443.192 (5)138
C8—H8A···O5iv0.962.683.280 (6)121
C11—H11···O5v0.932.673.312 (5)127
C1—H1···O5vi0.932.623.441 (6)148
Symmetry codes: (ii) x+1, y−1, z−1; (iii) x−1, y, z; (iv) −x+1, −y+2, −z+2; (v) −x+2, −y+1, −z+1; (vi) −x+2, −y+2, −z+2.
Table 1
Selected geometric parameters (Å) top
V1—O31.898 (3)V1—O4i2.346 (3)
V1—O41.657 (3)V1—N12.148 (3)
V1—O51.610 (3)V1—N22.245 (3)
Symmetry codes: (i) −x+2, −y+2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C10—H10···O1ii0.932.483.393 (6)168
C16—H16···O4iii0.932.443.192 (5)138
C8—H8A···O5iv0.962.683.280 (6)121
C11—H11···O5v0.932.673.312 (5)127
C1—H1···O5vi0.932.623.441 (6)148
Symmetry codes: (ii) x+1, y−1, z−1; (iii) x−1, y, z; (iv) −x+1, −y+2, −z+2; (v) −x+2, −y+1, −z+1; (vi) −x+2, −y+2, −z+2.
Acknowledgements top

The authors thank the Natural Science Foundation of Shandong Province (No. Y2004B02) for a research grant.

references
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