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The green crystals of the title compound, [V(C22H18N2O2)O], represent a mononuclear oxovanadium complex. The central VIV centre has a distorted square-pyramidal coordination. Two N atoms and two O atoms of the Schiff base ligand define the base of the pyramid, and the oxide O atom is in the apical position. Density functional theory (DFT) calculations were performed to analyse the changes in the geometry of the ligand during the complex formation. The most significant changes are observed in the values of the torsion angles in the vicinity of the donor N atoms. The HOMA index (Harmonic Oscillator Model of Aromaticity) has been calculated to compare the aromaticity of the benzene rings in the complex and its ligand.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111028277/ku3049sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270111028277/ku3049Isup2.hkl
Contains datablock I

CCDC reference: 846625

Comment top

The most important oxidovanadium(IV) compounds are those containing Schiff base units as ligands, and numerous complexes of these combinations have been prepared and studied (Mohebbi & Bakhshi, 2008; Kasumov et al., 2010). There is an extensive literature on their application in some important industrial and life processes (Chang et al., 1997; Mohammadi & Yazdanparast, 2009; Boghaei et al., 2006). They are interesting because of their antitumour and antiviral properties (Meshkini & Yazdanparast, 2010; Rehder, 2003); it was also demonstrated that they can show antioxidant activity (Mohammadi & Yazdanparast, 2010) and be applied as catalysts (Ben Zid et al., 2010). The oxide functionality of oxidovanadium complexes has taken part in a number of oxide-transfer reactions (Adão et al., 2009). Some of the important features of these compounds are their preparative accessibility, diversity and structural variability, which make them very attractive. All of these facts have convinced us to look for new oxidovanadium(IV) complexes with Schiff bases. We report here the preparation and the crystal and molecular structure of the oxidovanadium complex oxido{2,2'-[1,1'-(o-phenylenedinitrilo)diethanylylidyne]diphenolato}vanadium(IV), [V(acetph)O], (I), with a VO(N2O2) coordination model. A brown form of the [V(acetph)O] complex has been obtained by Boghaei & Mohebi (2002).

A view of the molecular structure of the complex and its atom-numbering scheme is shown in Fig. 1. The X-ray analysis (single-crystal) of the complex established that both hydroxy groups are deprotonated and coordinated. It means that acetph is a doubly negative quadridentate ligand. To aid structural data analysis, the molecular geometry of (I) was optimized using quantum-mechanical density functional theory (DFT) calculations. The resultant equilibrium structure of (I) in the gas phase is nonplanar with a mirror plane which is perpendicular to the phenyl ring (C9–C14) and passes through the V1 and O3 (Cs point-group symmetry). The oxidovanadium(IV) atom is coordinated in a square-pyramidal geometry by two N atoms and two O atoms from a ligand. The relevant bond lengths and angles are given in Table 2. The bond lengths to vanadium were in the range accepted for many other vanadium Schiff base complexes found in the Cambridge Structural Database (CSD; Allen, 2002). The VO bond length of 1.5913 (11) Å is also in good agreement with those observed for other five-coordinate vanadium compounds [average literature values for V—N, V—O and VO bond lengths are 2.06 (2), 1.93 (1) and 1.60 (1) Å respectively]. The V atom is located 0.6328 (7) Å in the X-ray structure and 0.6737 Å in the calculated structure above the best N2O2 least-squares plane of the Schiff base. This value lies in the range observed for other five-coordinate oxidovanadium compounds 0.567–0.692Å (CSD; Allen, 2002). There are no significant differences between the values of the bond lengths and angles of (I) in the solid-state (X-ray) and calculated structure. The differences do not exceed 0.04 Å for bond distances, 3° for bond angles and 10° for torsion angles. The VO bond axis is tilted 1.1° from the normal to the plane defined by N2O2 donor atoms, whereas in the analogous five-coordinated oxidovanadium(IV) complexes it is in the range 1.35–5.693°. The crystal structure of (I) is presented in Fig. 2. The complex molecules are held together through weak hydrogen bonds. The parameters of these interactions are given in Table 1. The first bond is situated between the H atom of the phenyl ring (C3—H3···O3) and the oxide O atom. The second is located between the H atom of the methyl group and the O atom of the donor group (C16—H16···O2). The latest hydrogen bond forms a network of dimers where two axial O atoms of the molecules are directed back to each other. Moreover, the C3—H3···O3 bond holds together two neighbouring dimers.

Another aim of our studies was to find the differences in the geometry and π-electron delocalization of (I) and its ligand. Unfortunately, the X-ray molecular structure of the ligand is not known. The crystallization of the ligand has been performed many times in different solvents, but in each case the crystals were not suitable for the X-ray analysis. It was the reason, why the molecular geometry of the ligand was obtained using the quantum-mechanical calculations. The DFT study also predicts nonplanar Cs point symmetry as the preferential one for the isolated ligand molecule (Fig. 1b). The ligand molecule is stabilized by two intramolecular O—H···N hydrogen bonds which form extra six-membered quasi-rings. A extra quasi-ring can be considered as a quasi-aromatic ring which contains a hydrogen atom in a ligand, or a metal ion in a complex. The resulting rings can be investigated as molecular patterns of intramolecular resonance-assisted hydrogen bonds. The position of the extra ring formed by the substituents interacting through the hydrogen bond is found to influence both the strength of the hydrogen bond, and the local aromaticity of the polycyclic aromatic hydrocarbon (PAH) skeleton. Relatively, a greater loss of aromaticity of the ipso-ring (phenyl ring) can be observed for these kinked-like structures because of the larger participation of π-electrons coming from the ipso-ring in the formation of the quasi-ring (Krygowski et al., 2010; Palusiak et al., 2009). From the geometry point of view, the extent of π-electron delocalization can be deduced from the bond lengths of the ring (CC-bond lengths) using the Harmonic Oscillator Model of Aromaticity (HOMA) (Kruszewski & Krygowski, 1973; Krygowski, 1993) The HOMA values of the phenyl rings with the quasi-rings in the ligand molecules are: 0.904 for C1–C6 and for C16–C21, and decreases to 0.874 (C1–C6) and 0.900 (C16–C21) in the X-ray structure of (I) and 0.778 (C1–C6 and C16–C21) in the calculated geometry of (I), whereas in ligand and (I) the values of the aromaticity parameters for the C9–C14 ring are significantly higher and equal to 0.959, 0.982 (X-ray) 0.962 (DFT), respectively. The formation of the complex causes changes in the conformation of the ligand molecule. Firstly, the planarity of the ligand increases as the result of the complex formation. The values of the angles between planes defined by four donor atoms (N2O2) and planes of benzene rings are decreased in the following order: from 51.11 (ligand) to 21.11 (7) (X-ray) and 22.10° (DFT) in (I) for the C1–C6 ring, from 40.78 (ligand) to 16.98 (8) (X-ray) and 24.00° (DFT) in (I) for C9–C14, and from 51.11 (ligand) to 11.06 (8) (X-ray) and 22.10° (DFT) in (I) for C17–C22. The other consequences of complex forming are changes in the values of torsion angles. The most noticeable changes in (I) (in the X-ray and DFT structures) are found for the following torsion angles: C9—N1—C7—C6, C7—N1—C9—C14, C15—N2—C14—C9 and C14—N2—C15—C17 (Table 1). All of these angles are in environment of the N1 and N2 atoms but the turnover does not concern the CN double bond.

Related literature top

For related literature, see: Adão, Pessoa, Henriques, Kuznetsov, Avecilla, Maurya, Kumar & Correia (2009); Allen (2002); Becke (1988, 1993); Ben Zid, Khedher & Ghorbel (2010); Boghaei & Mohebi (2002); Boghaei et al. (2006); Chang et al. (1997); Farmer & Urbach (1970); Frisch et al. (2010); Kasumov et al. (2010); Kruszewski & Krygowski (1973); Krygowski (1993); Krygowski et al. (2010); Lee et al. (1988); Meshkini & Yazdanparast (2010); Mohammadi & Yazdanparast (2009, 2010); Mohebbi & Bakhshi (2008); Palusiak et al. (2009); Rehder (2003).

Experimental top

The crude brown powder of (I) (Boghaei & Mohebi, 2002) was prepared according to the procedure published by Farmer & Urbach (1970). Crystals of (I) suitable for X-ray crystal structure analysis were grown from MeOH. The quantum-mechanical caclucations were performed using standard DFT and employed the B3LYP hybrid functional (Becke, 1988, 1993; Lee et al., 1988) with the 6–311++G(d,p) level of theory. All species corresponded to the minima at the B3LYP/6–311++G(d,p) level with no imaginary frequencies. All calculations were performed using the GAUSSIAN09 program package (Frisch et al., 2010).

Refinement top

All H atoms were generated in idealized positions, viz. C—H = 0.96 Å, tetrahedral angles and Uiso(H) = 1.5Ueq(C) for methyl groups, and C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic H atoms. Only H-atom coordinates were refined.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure (a) of (I), showing 50% displacement ellipsoids (arbitrary spheres for the H atoms), and (b) of the ligand calculated by DFT. Dashed lines indicate intramolecular hydrogen bonds.
[Figure 2] Fig. 2. The packing diagram of (I), showing the C—H···O hydrogen bonds between the complex molecules (dashed lines).
{2,2'-[1,1'-(o-phenylenedinitrilo)bis(ethan-1-yl-1- ylidene)]diphenolato}oxovanadium(IV) top
Crystal data top
[V(C22H18N2O2)O]F(000) = 844
Mr = 409.32Dx = 1.507 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 11176 reflections
a = 9.3715 (2) Åθ = 3.0–25.0°
b = 14.2178 (2) ŵ = 0.58 mm1
c = 13.8932 (2) ÅT = 293 K
β = 102.867 (2)°Plate, green
V = 1804.68 (5) Å30.21 × 0.18 × 0.16 mm
Z = 4
Data collection top
Oxford Diffraction Xcalibur
diffractometer
2872 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.015
Graphite monochromatorθmax = 25.0°, θmin = 3.0°
Detector resolution: 1024 pixels mm-1h = 1110
ω scansk = 1614
11176 measured reflectionsl = 1616
3167 independent reflections
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)] = 0.024Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.073Only H-atom coordinates refined
S = 1.07 w = 1/[σ2(Fo2) + (0.044P)2 + 0.5075P]
where P = (Fo2 + 2Fc2)/3
3167 reflections(Δ/σ)max = 0.001
307 parametersΔρmax = 0.21 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
[V(C22H18N2O2)O]V = 1804.68 (5) Å3
Mr = 409.32Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.3715 (2) ŵ = 0.58 mm1
b = 14.2178 (2) ÅT = 293 K
c = 13.8932 (2) Å0.21 × 0.18 × 0.16 mm
β = 102.867 (2)°
Data collection top
Oxford Diffraction Xcalibur
diffractometer
2872 reflections with I > 2σ(I)
11176 measured reflectionsRint = 0.015
3167 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0240 restraints
wR(F2) = 0.073Only H-atom coordinates refined
S = 1.07Δρmax = 0.21 e Å3
3167 reflectionsΔρmin = 0.26 e Å3
307 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
V10.55364 (2)0.075886 (17)0.733235 (18)0.02510 (10)
O10.74948 (11)0.11592 (8)0.73603 (9)0.0353 (3)
O20.51093 (12)0.12567 (8)0.60217 (8)0.0375 (3)
O30.48286 (12)0.14085 (8)0.80343 (9)0.0426 (3)
N10.64589 (13)0.03791 (9)0.81843 (9)0.0268 (3)
N20.40308 (13)0.03095 (8)0.67925 (9)0.0260 (3)
C10.87759 (16)0.08774 (10)0.78680 (12)0.0284 (3)
C21.00057 (18)0.14262 (12)0.78036 (14)0.0395 (4)
H20.986 (2)0.1972 (15)0.7382 (14)0.047*
C31.13956 (18)0.11605 (13)0.82570 (15)0.0420 (4)
H31.222 (2)0.1542 (14)0.8186 (15)0.050*
C41.16285 (18)0.03473 (13)0.88182 (14)0.0392 (4)
H41.259 (2)0.0182 (14)0.9148 (14)0.047*
C51.04632 (17)0.02008 (12)0.88968 (12)0.0343 (4)
H51.064 (2)0.0775 (13)0.9272 (15)0.041*
C60.90056 (16)0.00331 (10)0.84205 (11)0.0276 (3)
C70.78379 (16)0.06238 (10)0.84742 (11)0.0272 (3)
C80.8277 (2)0.16078 (12)0.88147 (14)0.0376 (4)
H8A0.749 (2)0.2051 (15)0.8608 (15)0.056*
H8B0.857 (2)0.1636 (15)0.9525 (17)0.056*
H8C0.913 (2)0.1834 (15)0.8548 (15)0.056*
C90.52995 (17)0.09752 (10)0.83256 (11)0.0290 (3)
C100.5300 (2)0.14546 (12)0.91998 (13)0.0392 (4)
H100.607 (2)0.1406 (14)0.9739 (15)0.047*
C110.4094 (2)0.19768 (13)0.92931 (14)0.0444 (4)
H110.409 (2)0.2295 (15)0.9880 (15)0.053*
C120.28730 (19)0.20106 (12)0.85256 (13)0.0398 (4)
H120.198 (2)0.2361 (14)0.8599 (13)0.048*
C130.28269 (17)0.14958 (11)0.76768 (13)0.0337 (3)
H130.196 (2)0.1472 (13)0.7151 (14)0.040*
C140.40359 (17)0.09721 (10)0.75639 (11)0.0275 (3)
C150.32490 (15)0.04205 (11)0.58911 (11)0.0283 (3)
C160.2599 (2)0.13533 (12)0.55079 (14)0.0391 (4)
H16A0.308 (2)0.1844 (17)0.5912 (16)0.059*
H16B0.276 (2)0.1445 (15)0.4898 (17)0.059*
H16C0.153 (3)0.1353 (15)0.5486 (16)0.059*
C170.30164 (16)0.03622 (11)0.52007 (11)0.0295 (3)
C180.17937 (19)0.03406 (13)0.43926 (12)0.0386 (4)
H180.119 (2)0.0176 (14)0.4329 (14)0.046*
C190.1480 (2)0.10688 (14)0.37328 (12)0.0421 (4)
H190.060 (2)0.1028 (14)0.3212 (15)0.051*
C200.2425 (2)0.18310 (13)0.38188 (12)0.0407 (4)
H200.224 (2)0.2327 (14)0.3369 (14)0.049*
C210.36363 (19)0.18700 (12)0.45822 (12)0.0369 (4)
H210.427 (2)0.2401 (15)0.4656 (13)0.044*
C220.39395 (16)0.11595 (11)0.53024 (11)0.0295 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.02225 (15)0.02103 (15)0.03097 (16)0.00055 (9)0.00368 (11)0.00008 (9)
O10.0248 (5)0.0298 (6)0.0491 (7)0.0011 (4)0.0037 (5)0.0105 (5)
O20.0356 (6)0.0357 (6)0.0366 (6)0.0084 (5)0.0015 (5)0.0093 (5)
O30.0356 (6)0.0396 (7)0.0537 (7)0.0004 (5)0.0123 (6)0.0128 (6)
N10.0266 (6)0.0252 (6)0.0281 (6)0.0023 (5)0.0052 (5)0.0020 (5)
N20.0245 (6)0.0235 (6)0.0305 (6)0.0005 (5)0.0068 (5)0.0001 (5)
C10.0240 (7)0.0263 (7)0.0352 (8)0.0001 (6)0.0070 (6)0.0037 (6)
C20.0308 (8)0.0314 (9)0.0569 (11)0.0032 (7)0.0108 (8)0.0034 (8)
C30.0262 (8)0.0378 (9)0.0631 (12)0.0048 (7)0.0120 (8)0.0077 (8)
C40.0235 (8)0.0413 (10)0.0502 (10)0.0033 (7)0.0023 (7)0.0100 (8)
C50.0306 (8)0.0340 (8)0.0358 (8)0.0047 (7)0.0019 (7)0.0026 (7)
C60.0263 (7)0.0275 (7)0.0282 (7)0.0009 (6)0.0047 (6)0.0043 (6)
C70.0298 (8)0.0271 (8)0.0239 (7)0.0011 (6)0.0042 (6)0.0007 (6)
C80.0375 (9)0.0295 (8)0.0436 (10)0.0026 (7)0.0042 (8)0.0073 (7)
C90.0293 (8)0.0250 (7)0.0336 (8)0.0025 (6)0.0091 (6)0.0016 (6)
C100.0397 (9)0.0415 (9)0.0357 (9)0.0046 (7)0.0071 (7)0.0084 (7)
C110.0494 (10)0.0431 (10)0.0448 (10)0.0040 (8)0.0189 (8)0.0135 (8)
C120.0377 (9)0.0338 (9)0.0528 (10)0.0052 (7)0.0206 (8)0.0049 (8)
C130.0280 (8)0.0320 (8)0.0425 (9)0.0030 (6)0.0113 (7)0.0016 (7)
C140.0291 (7)0.0228 (7)0.0321 (8)0.0011 (6)0.0102 (6)0.0003 (6)
C150.0236 (7)0.0294 (8)0.0330 (8)0.0008 (6)0.0083 (6)0.0055 (6)
C160.0455 (10)0.0323 (9)0.0393 (9)0.0090 (7)0.0088 (8)0.0084 (7)
C170.0295 (8)0.0314 (8)0.0275 (7)0.0031 (6)0.0065 (6)0.0039 (6)
C180.0365 (9)0.0448 (10)0.0320 (8)0.0021 (8)0.0022 (7)0.0073 (7)
C190.0393 (9)0.0556 (11)0.0277 (8)0.0118 (8)0.0003 (7)0.0042 (8)
C200.0508 (10)0.0402 (9)0.0300 (8)0.0148 (8)0.0070 (7)0.0037 (7)
C210.0449 (9)0.0314 (8)0.0337 (8)0.0033 (7)0.0071 (7)0.0029 (7)
C220.0307 (8)0.0297 (8)0.0280 (7)0.0040 (6)0.0064 (6)0.0018 (6)
Geometric parameters (Å, º) top
V1—O31.5913 (11)C9—C101.393 (2)
V1—O21.9111 (11)C9—C141.401 (2)
V1—O11.9137 (11)C10—C111.383 (2)
V1—N12.0761 (12)C10—H100.92 (2)
V1—N22.0951 (12)C11—C121.380 (3)
O1—C11.3124 (18)C11—H110.93 (2)
O2—C221.3159 (18)C12—C131.380 (2)
N1—C71.3121 (19)C12—H121.00 (2)
N1—C91.4256 (19)C13—C141.394 (2)
N2—C151.3120 (19)C13—H130.967 (19)
N2—C141.4260 (19)C15—C171.454 (2)
C1—C21.411 (2)C15—C161.506 (2)
C1—C61.415 (2)C16—H16A0.95 (2)
C2—C31.368 (2)C16—H16B0.90 (2)
C2—H20.96 (2)C16—H16C0.99 (2)
C3—C41.384 (3)C17—C221.414 (2)
C3—H30.97 (2)C17—C181.415 (2)
C4—C51.366 (2)C18—C191.371 (3)
C4—H40.94 (2)C18—H180.92 (2)
C5—C61.418 (2)C19—C201.388 (3)
C5—H50.962 (19)C19—H190.97 (2)
C6—C71.453 (2)C20—C211.371 (2)
C7—C81.505 (2)C20—H200.93 (2)
C8—H8A0.96 (2)C21—C221.406 (2)
C8—H8B0.96 (2)C21—H210.95 (2)
C8—H8C1.01 (2)
O3—V1—O2109.97 (6)C10—C9—C14119.75 (14)
O3—V1—O1110.10 (6)C10—C9—N1123.97 (15)
O2—V1—O184.58 (5)C14—C9—N1115.84 (13)
O3—V1—N1106.28 (6)C11—C10—C9120.20 (17)
O2—V1—N1143.52 (5)C11—C10—H10118.3 (12)
O1—V1—N186.82 (5)C9—C10—H10121.4 (12)
O3—V1—N2107.51 (5)C12—C11—C10120.05 (16)
O2—V1—N286.90 (5)C12—C11—H11119.6 (12)
O1—V1—N2142.12 (5)C10—C11—H11120.3 (12)
N1—V1—N278.51 (5)C11—C12—C13120.30 (15)
C1—O1—V1132.72 (10)C11—C12—H12120.5 (11)
C22—O2—V1130.31 (10)C13—C12—H12119.0 (11)
C7—N1—C9121.93 (12)C12—C13—C14120.53 (16)
C7—N1—V1129.66 (10)C12—C13—H13121.6 (11)
C9—N1—V1107.96 (9)C14—C13—H13117.8 (11)
C15—N2—C14123.06 (12)C13—C14—C9118.99 (14)
C15—N2—V1128.12 (10)C13—C14—N2124.81 (14)
C14—N2—V1108.70 (9)C9—C14—N2115.50 (13)
O1—C1—C2117.35 (14)N2—C15—C17120.50 (13)
O1—C1—C6124.13 (13)N2—C15—C16122.63 (15)
C2—C1—C6118.40 (14)C17—C15—C16116.83 (14)
C3—C2—C1121.71 (17)C15—C16—H16A109.7 (13)
C3—C2—H2119.6 (12)C15—C16—H16B108.7 (14)
C1—C2—H2118.4 (12)H16A—C16—H16B107.0 (19)
C2—C3—C4120.31 (16)C15—C16—H16C109.7 (13)
C2—C3—H3119.9 (12)H16A—C16—H16C111.3 (18)
C4—C3—H3119.8 (12)H16B—C16—H16C110.4 (19)
C5—C4—C3119.54 (15)C22—C17—C18117.79 (15)
C5—C4—H4120.7 (12)C22—C17—C15123.33 (13)
C3—C4—H4119.7 (12)C18—C17—C15118.88 (14)
C4—C5—C6122.22 (16)C19—C18—C17121.97 (17)
C4—C5—H5119.0 (12)C19—C18—H18120.1 (12)
C6—C5—H5118.7 (12)C17—C18—H18117.9 (12)
C1—C6—C5117.79 (14)C18—C19—C20119.64 (16)
C1—C6—C7123.20 (13)C18—C19—H19118.3 (12)
C5—C6—C7118.91 (14)C20—C19—H19122.1 (12)
N1—C7—C6121.02 (13)C21—C20—C19120.05 (16)
N1—C7—C8121.64 (14)C21—C20—H20119.1 (12)
C6—C7—C8117.23 (13)C19—C20—H20120.8 (12)
C7—C8—H8A112.1 (13)C20—C21—C22121.52 (17)
C7—C8—H8B110.9 (13)C20—C21—H21120.3 (11)
H8A—C8—H8B107.6 (17)C22—C21—H21118.1 (11)
C7—C8—H8C111.5 (12)O2—C22—C21117.85 (14)
H8A—C8—H8C107.4 (18)O2—C22—C17123.22 (14)
H8B—C8—H8C107.1 (17)C21—C22—C17118.88 (14)
O3—V1—O1—C195.90 (15)C1—C6—C7—C8161.77 (15)
O2—V1—O1—C1154.80 (15)C5—C6—C7—C814.6 (2)
N1—V1—O1—C110.28 (14)C7—N1—C9—C1044.5 (2)
N2—V1—O1—C176.93 (16)V1—N1—C9—C10142.46 (14)
O3—V1—O2—C2283.19 (14)C7—N1—C9—C14143.12 (14)
O1—V1—O2—C22167.37 (14)V1—N1—C9—C1429.93 (15)
N1—V1—O2—C2290.20 (15)C14—C9—C10—C114.2 (3)
N2—V1—O2—C2224.32 (13)N1—C9—C10—C11176.35 (16)
O3—V1—N1—C7114.23 (13)C9—C10—C11—C121.2 (3)
O2—V1—N1—C772.25 (16)C10—C11—C12—C132.5 (3)
O1—V1—N1—C74.21 (13)C11—C12—C13—C143.1 (3)
N2—V1—N1—C7140.68 (14)C12—C13—C14—C90.1 (2)
O3—V1—N1—C973.43 (10)C12—C13—C14—N2170.01 (15)
O2—V1—N1—C9100.09 (11)C10—C9—C14—C133.6 (2)
O1—V1—N1—C9176.55 (10)N1—C9—C14—C13176.33 (13)
N2—V1—N1—C931.66 (9)C10—C9—C14—N2167.28 (14)
O3—V1—N2—C15109.36 (13)N1—C9—C14—N25.46 (19)
O2—V1—N2—C150.61 (13)C15—N2—C14—C1335.0 (2)
O1—V1—N2—C1577.70 (15)V1—N2—C14—C13148.58 (13)
N1—V1—N2—C15147.00 (13)C15—N2—C14—C9154.70 (14)
O3—V1—N2—C1474.49 (10)V1—N2—C14—C921.68 (15)
O2—V1—N2—C14175.54 (9)C14—N2—C15—C17165.67 (13)
O1—V1—N2—C1498.45 (11)V1—N2—C15—C1718.7 (2)
N1—V1—N2—C1429.15 (9)C14—N2—C15—C1616.5 (2)
V1—O1—C1—C2171.12 (12)V1—N2—C15—C16159.16 (12)
V1—O1—C1—C613.0 (2)N2—C15—C17—C2221.5 (2)
O1—C1—C2—C3176.00 (16)C16—C15—C17—C22156.47 (15)
C6—C1—C2—C30.1 (3)N2—C15—C17—C18157.38 (14)
C1—C2—C3—C41.7 (3)C16—C15—C17—C1824.7 (2)
C2—C3—C4—C51.6 (3)C22—C17—C18—C191.2 (2)
C3—C4—C5—C60.0 (3)C15—C17—C18—C19177.72 (15)
O1—C1—C6—C5177.23 (14)C17—C18—C19—C203.7 (3)
C2—C1—C6—C51.4 (2)C18—C19—C20—C212.4 (3)
O1—C1—C6—C70.8 (2)C19—C20—C21—C221.3 (3)
C2—C1—C6—C7175.01 (15)V1—O2—C22—C21154.48 (12)
C4—C5—C6—C11.5 (2)V1—O2—C22—C1728.1 (2)
C4—C5—C6—C7175.09 (15)C20—C21—C22—O2178.79 (15)
C9—N1—C7—C6173.29 (13)C20—C21—C22—C173.7 (2)
V1—N1—C7—C615.3 (2)C18—C17—C22—O2179.80 (14)
C9—N1—C7—C810.6 (2)C15—C17—C22—O21.3 (2)
V1—N1—C7—C8160.83 (12)C18—C17—C22—C212.4 (2)
C1—C6—C7—N114.5 (2)C15—C17—C22—C21178.68 (14)
C5—C6—C7—N1169.09 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O3i0.97 (2)2.51 (2)3.319 (2)141.5 (16)
C8—H8C···O2ii1.01 (2)2.84 (2)3.377 (2)114.3 (15)
C16—H16B···O2iii0.90 (2)2.61 (2)3.344 (2)138.6 (18)
Symmetry codes: (i) x+1, y, z; (ii) x+3/2, y1/2, z+3/2; (iii) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula[V(C22H18N2O2)O]
Mr409.32
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)9.3715 (2), 14.2178 (2), 13.8932 (2)
β (°) 102.867 (2)
V3)1804.68 (5)
Z4
Radiation typeMo Kα
µ (mm1)0.58
Crystal size (mm)0.21 × 0.18 × 0.16
Data collection
DiffractometerOxford Diffraction Xcalibur
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
11176, 3167, 2872
Rint0.015
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.024, 0.073, 1.07
No. of reflections3167
No. of parameters307
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.21, 0.26

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O3i0.97 (2)2.51 (2)3.319 (2)141.5 (16)
C8—H8C···O2ii1.01 (2)2.84 (2)3.377 (2)114.3 (15)
C16—H16B···O2iii0.90 (2)2.61 (2)3.344 (2)138.6 (18)
Symmetry codes: (i) x+1, y, z; (ii) x+3/2, y1/2, z+3/2; (iii) x+1, y, z+1.
Selected geometric parameters for (I) (X-ray and DFT) and the ligand molecule (DFT) (Å, °) top
(I) X-ray(I) DFTLigand DFT
V1–O31.5913 (11)1.5825
V1–O21.9111 (11)1.9335
V1–O11.9137 (11)1.9335
V1–N12.0761 (12)2.1116
V1–N22.0951 (12)2.1116
O3–V1–O2109.97 (6)111.74
O3–V1–O1110.10 (6)111.74
O2–V1–O184.58 (5)87.00
O3–V1–N1106.28 (6)107.10
O2–V1–N1143.52 (5)140.53
O1–V1–N186.82 (5)85.12
O3–V1–N2107.51 (5)107.10
O2–V1–N286.90 (5)85.12
O1–V1–N2142.12 (5)140.53
N1–V1–N278.51 (5)76.99
O1–C1–C6–C70.8 (2)-5.30.5
C1–C6–C7–N1-14.5 (2)-10.5-1.0
C9–N1–C7–C6-173.3 (1)-169.0175.2
C7–N1–C9–C14-143.1 (1)-145.1117.2
N1–C9–C14–N2-5.5 (2)0.00.0
C15–N2–C14–C9154.7 (1)145.1-117.2
C14–N2–C15–C17165.7 (1)169.0-175.2
N2–C15–C17–C2221.5 (2)10.51.0
C15–C17–C22–O21.3 (2)5.3-0.5
 

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