Skip to main content
NCBI home page
Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2011 Apr 29;67(Pt 5):m650. doi: 10.1107/S1600536811015406

(Acetyl­acetonato-κ2 O,O′)(2-bromo-4-chloro-6-{[2-(dimethyl­amino)­ethyl­imino]­meth­yl}phenolato-κ3 N,N′,O)oxidovanadium(IV)

Fu-Ming Wang a,*
PMCID: PMC3089186  PMID: 21754355

Abstract

The VIV atom in the title complex, [V(C11H13BrClN2O)(C5H7O2)O], is six-coordinated by one phenolate O, one imino N and one amino N atom of the tridentate anionic Schiff base ligand, by one oxide O atom, and by two O atoms of an acetyl­acetonate anion, forming a distorted cis-VN2O4 octa­hedral coordination geometry. The deviation of the V atom from the plane defined by the three donor atoms of the Schiff base ligand and one O atom of the acetyl­acetone ligand towards the oxide O atom is 0.256 (2) Å.

Related literature

For background to oxidovanadium complexes, see: Hiromura et al. (2007 ▶); Seena et al. (2008 ▶); Rosenthal et al. (2008 ▶); Kurup et al. (2010 ▶). For similar oxidovanadium complexes with Schiff bases, see: Li et al. (1988 ▶); Cornman et al. (1992 ▶); Smith et al. (2000 ▶); Sarkar & Pal (2006 ▶).graphic file with name e-67-0m650-scheme1.jpg

Experimental

Crystal data

  • [V(C11H13BrClN2O)(C5H7O2)O]

  • M r = 470.64

  • Orthorhombic, Inline graphic

  • a = 20.351 (2) Å

  • b = 12.749 (1) Å

  • c = 7.410 (2) Å

  • V = 1922.6 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.76 mm−1

  • T = 298 K

  • 0.37 × 0.33 × 0.32 mm

Data collection

  • Bruker SMART CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.429, T max = 0.473

  • 7060 measured reflections

  • 3863 independent reflections

  • 2284 reflections with I > 2σ(I)

  • R int = 0.052

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047

  • wR(F 2) = 0.100

  • S = 0.93

  • 3863 reflections

  • 230 parameters

  • 1 restraint

  • H-atom parameters constrained

  • Δρmax = 0.32 e Å−3

  • Δρmin = −0.39 e Å−3

  • Absolute structure: Flack (1983 ▶), 1475 Friedel pairs

  • Flack parameter: 0.028 (14)

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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015406/hb5858sup1.cif

e-67-0m650-sup1.cif (17.8KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015406/hb5858Isup2.hkl

e-67-0m650-Isup2.hkl (189.4KB, hkl)

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

Table 1. Selected geometric parameters (Å, °).

V1—O4 1.598 (4)
V1—O1 1.952 (4)
V1—O3 1.988 (4)
V1—N1 2.078 (5)
V1—O2 2.168 (4)
V1—N2 2.222 (5)
Open in a new tab
O4—V1—O1 100.0 (2)
O4—V1—O3 98.39 (19)
O1—V1—O3 88.92 (17)
O4—V1—N1 99.13 (19)
O1—V1—N1 88.30 (18)
O3—V1—N1 162.47 (18)
O4—V1—O2 173.0 (2)
O1—V1—O2 86.82 (17)
O3—V1—O2 82.86 (15)
N1—V1—O2 79.70 (17)
O4—V1—N2 91.3 (2)
O1—V1—N2 165.2 (2)
O3—V1—N2 98.79 (17)
N1—V1—N2 80.5 (2)
O2—V1—N2 81.70 (17)
Open in a new tab

Acknowledgments

This work was supported financially by Dezhou University, People’s Republic of China.

supplementary crystallographic information

Comment

Oxovanadium complexes have received much attention due to their structures and biological properties (Hiromura et al., 2007; Seena et al., 2008; Rosenthal et al., 2008; Kurup et al., 2010). In this paper, the title new oxovanadium(IV) complex, (I), with a Schiff base ligand is reported.

The VIV atom in the title complex, Fig. 1, is six-coordinated by one phenolic O, one imino N, and one amino N atoms of the Schiff base ligand, by one oxo O atom, and by two O atoms of an acetylacetone ligand, forming a distorted octahedral geometry. The deviation of the V atom from the plane defined by the three donor atoms of the Schiff base ligand and one O atom of the acetylacetone ligand towards the oxo O atom is 0.256 (2) Å. The coordinate bond lengths and angles (Table 1) are comparable with those observed in similar oxovanadium(IV) complexes with Schiff bases and acetylacetone ligands (Li et al., 1988; Cornman et al., 1992; Smith et al., 2000; Sarkar & Pal, 2006).

Experimental

3-Bromo-5-chlorosalicylaldehyde (1 mmol, 0.23 g), N,N-dimethylethane-1,2-diamine (1 mmol, 0.09 g), and VO(acac)2 (1 mmol, 0.26 g) were mixed in methanol (30 ml). The mixture was boiled under reflux for 2 h, then cooled to room temperature. Green blocks of (I) were formed after slow evaporation of the solution in air for a few days.

Refinement

Hydrogen atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.93–0.97 Å, and with Uiso(H) set at 1.2Ueq(C) and 1.5Ueq(Cmethyl).

Figures

Fig. 1.

Fig. 1.

Open in a new tab

The molecular structure of the title compound, showing displacement ellipsoids drawn at the 30% probability level.

Crystal data

[V(C11H13BrClN2O)(C5H7O2)O] Dx = 1.626 Mg m−3
Mr = 470.64 Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21 Cell parameters from 1129 reflections
a = 20.351 (2) Å θ = 2.5–24.5°
b = 12.749 (1) Å µ = 2.76 mm−1
c = 7.410 (2) Å T = 298 K
V = 1922.6 (6) Å3 Block, green
Z = 4 0.37 × 0.33 × 0.32 mm
F(000) = 948
Open in a new tab

Data collection

Bruker SMART CCD diffractometer 3863 independent reflections
Radiation source: fine-focus sealed tube 2284 reflections with I > 2σ(I)
graphite Rint = 0.052
ω scans θmax = 27.5°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) h = −15→26
Tmin = 0.429, Tmax = 0.473 k = −10→16
7060 measured reflections l = −9→9
Open in a new tab

Refinement

Refinement on F2 Secondary atom site location: difference Fourier map
Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047 H-atom parameters constrained
wR(F2) = 0.100 w = 1/[σ2(Fo2)]
S = 0.93 (Δ/σ)max < 0.001
3863 reflections Δρmax = 0.32 e Å−3
230 parameters Δρmin = −0.39 e Å−3
1 restraint Absolute structure: Flack (1983), 1475 Friedel pairs
Primary atom site location: structure-invariant direct methods Flack parameter: 0.028 (14)
Open in a new tab

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.
Open in a new tab

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
V1 0.63268 (4) −0.04041 (7) 0.00361 (16) 0.0381 (3)
Br1 0.64969 (3) 0.21353 (5) −0.47589 (10) 0.0583 (2)
Cl1 0.51964 (10) 0.50695 (15) −0.0592 (3) 0.0756 (6)
N1 0.5724 (2) 0.0368 (4) 0.1869 (7) 0.0380 (12)
N2 0.6403 (2) −0.1505 (4) 0.2353 (7) 0.0439 (14)
O1 0.62782 (18) 0.0834 (3) −0.1510 (6) 0.0457 (11)
O2 0.70569 (18) 0.0442 (3) 0.1592 (5) 0.0476 (11)
O3 0.71095 (18) −0.0874 (3) −0.1350 (5) 0.0431 (10)
O4 0.57889 (17) −0.1130 (3) −0.0917 (6) 0.0538 (12)
C1 0.6018 (2) 0.1765 (5) −0.1231 (8) 0.0343 (14)
C2 0.6071 (3) 0.2535 (5) −0.2607 (8) 0.0376 (15)
C3 0.5833 (3) 0.3523 (6) −0.2406 (9) 0.0450 (17)
H3 0.5897 0.4019 −0.3310 0.054*
C4 0.5496 (3) 0.3788 (5) −0.0854 (10) 0.0501 (17)
C5 0.5398 (2) 0.3065 (5) 0.0468 (9) 0.0426 (15)
H5 0.5161 0.3248 0.1495 0.051*
C6 0.5652 (2) 0.2037 (4) 0.0296 (11) 0.0375 (12)
C7 0.5528 (3) 0.1311 (5) 0.1766 (8) 0.0402 (15)
H7 0.5280 0.1562 0.2728 0.048*
C8 0.5571 (3) −0.0253 (5) 0.3450 (10) 0.0534 (19)
H8A 0.5201 −0.0709 0.3202 0.064*
H8B 0.5456 0.0203 0.4449 0.064*
C9 0.6162 (3) −0.0896 (6) 0.3927 (9) 0.060 (2)
H9A 0.6509 −0.0436 0.4353 0.072*
H9B 0.6051 −0.1374 0.4898 0.072*
C10 0.7074 (3) −0.1882 (6) 0.2724 (10) 0.072 (2)
H10A 0.7069 −0.2319 0.3779 0.108*
H10B 0.7359 −0.1294 0.2923 0.108*
H10C 0.7230 −0.2280 0.1711 0.108*
C11 0.5987 (3) −0.2457 (5) 0.2077 (13) 0.076 (2)
H11A 0.5551 −0.2247 0.1734 0.113*
H11B 0.5967 −0.2852 0.3179 0.113*
H11C 0.6174 −0.2883 0.1142 0.113*
C12 0.8031 (3) 0.1328 (6) 0.2472 (10) 0.064 (2)
H12A 0.8117 0.0954 0.3572 0.097*
H12B 0.7777 0.1944 0.2733 0.097*
H12C 0.8439 0.1527 0.1923 0.097*
C13 0.7652 (3) 0.0633 (5) 0.1198 (9) 0.0422 (16)
C14 0.7966 (3) 0.0228 (5) −0.0327 (9) 0.0459 (18)
H14 0.8394 0.0447 −0.0556 0.055*
C15 0.7685 (3) −0.0473 (5) −0.1516 (9) 0.0459 (17)
C16 0.8073 (3) −0.0823 (6) −0.3127 (10) 0.069 (2)
H16A 0.7848 −0.0620 −0.4209 0.104*
H16B 0.8121 −0.1572 −0.3101 0.104*
H16C 0.8500 −0.0501 −0.3101 0.104*
Open in a new tab

Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
V1 0.0346 (4) 0.0410 (6) 0.0388 (6) 0.0030 (4) 0.0017 (5) −0.0003 (6)
Br1 0.0701 (4) 0.0680 (5) 0.0367 (3) −0.0054 (3) 0.0078 (4) −0.0003 (5)
Cl1 0.1159 (14) 0.0445 (11) 0.0665 (12) 0.0281 (11) 0.0116 (11) 0.0049 (10)
N1 0.031 (3) 0.041 (3) 0.042 (3) −0.001 (2) 0.006 (2) −0.001 (3)
N2 0.040 (3) 0.043 (4) 0.049 (3) 0.004 (3) 0.010 (2) 0.010 (3)
O1 0.057 (2) 0.043 (3) 0.038 (2) 0.014 (2) 0.018 (2) 0.004 (2)
O2 0.038 (2) 0.061 (3) 0.044 (3) −0.005 (2) 0.0084 (19) −0.012 (2)
O3 0.043 (2) 0.043 (3) 0.043 (3) 0.003 (2) 0.004 (2) −0.006 (2)
O4 0.042 (2) 0.053 (3) 0.066 (3) −0.002 (2) −0.012 (2) −0.005 (2)
C1 0.027 (3) 0.040 (4) 0.036 (4) −0.002 (3) −0.005 (2) −0.001 (3)
C2 0.036 (3) 0.042 (4) 0.035 (4) 0.000 (3) −0.002 (3) 0.002 (3)
C3 0.052 (4) 0.045 (5) 0.038 (4) −0.004 (3) −0.007 (3) 0.005 (3)
C4 0.053 (4) 0.042 (4) 0.056 (5) 0.005 (3) −0.011 (3) 0.000 (4)
C5 0.047 (3) 0.049 (4) 0.033 (4) 0.004 (3) −0.005 (3) −0.003 (4)
C6 0.032 (2) 0.040 (3) 0.041 (3) 0.003 (2) 0.006 (4) −0.001 (4)
C7 0.032 (3) 0.052 (5) 0.037 (4) 0.003 (3) 0.008 (3) −0.005 (3)
C8 0.052 (4) 0.045 (4) 0.063 (5) 0.006 (3) 0.027 (3) 0.017 (4)
C9 0.068 (4) 0.062 (5) 0.051 (5) 0.012 (4) 0.020 (4) 0.021 (4)
C10 0.053 (4) 0.076 (6) 0.087 (6) 0.019 (4) 0.008 (4) 0.029 (5)
C11 0.089 (5) 0.054 (5) 0.084 (6) −0.015 (4) −0.001 (5) 0.006 (5)
C12 0.055 (4) 0.065 (6) 0.073 (6) −0.008 (4) −0.011 (4) −0.017 (5)
C13 0.037 (4) 0.041 (4) 0.049 (4) 0.000 (3) 0.001 (3) 0.013 (3)
C14 0.032 (3) 0.050 (4) 0.056 (5) −0.001 (3) 0.009 (3) 0.006 (3)
C15 0.051 (4) 0.045 (5) 0.042 (4) 0.017 (4) 0.007 (3) 0.019 (4)
C16 0.069 (5) 0.090 (6) 0.049 (4) 0.010 (4) 0.030 (4) −0.001 (5)
Open in a new tab

Geometric parameters (Å, °)

V1—O4 1.598 (4) C6—C7 1.452 (9)
V1—O1 1.952 (4) C7—H7 0.9300
V1—O3 1.988 (4) C8—C9 1.497 (8)
V1—N1 2.078 (5) C8—H8A 0.9700
V1—O2 2.168 (4) C8—H8B 0.9700
V1—N2 2.222 (5) C9—H9A 0.9700
Br1—C2 1.885 (6) C9—H9B 0.9700
Cl1—C4 1.755 (7) C10—H10A 0.9600
N1—C7 1.268 (7) C10—H10B 0.9600
N1—C8 1.448 (8) C10—H10C 0.9600
N2—C10 1.473 (7) C11—H11A 0.9600
N2—C9 1.484 (8) C11—H11B 0.9600
N2—C11 1.494 (7) C11—H11C 0.9600
O1—C1 1.316 (6) C12—C13 1.507 (8)
O2—C13 1.269 (6) C12—H12A 0.9600
O3—C15 1.285 (7) C12—H12B 0.9600
C1—C6 1.399 (9) C12—H12C 0.9600
C1—C2 1.420 (8) C13—C14 1.397 (8)
C2—C3 1.358 (8) C14—C15 1.379 (8)
C3—C4 1.381 (8) C14—H14 0.9300
C3—H3 0.9300 C15—C16 1.499 (9)
C4—C5 1.360 (8) C16—H16A 0.9600
C5—C6 1.414 (7) C16—H16B 0.9600
C5—H5 0.9300 C16—H16C 0.9600
O4—V1—O1 100.0 (2) C6—C7—H7 116.7
O4—V1—O3 98.39 (19) N1—C8—C9 108.6 (5)
O1—V1—O3 88.92 (17) N1—C8—H8A 110.0
O4—V1—N1 99.13 (19) C9—C8—H8A 110.0
O1—V1—N1 88.30 (18) N1—C8—H8B 110.0
O3—V1—N1 162.47 (18) C9—C8—H8B 110.0
O4—V1—O2 173.0 (2) H8A—C8—H8B 108.4
O1—V1—O2 86.82 (17) N2—C9—C8 111.4 (6)
O3—V1—O2 82.86 (15) N2—C9—H9A 109.3
N1—V1—O2 79.70 (17) C8—C9—H9A 109.3
O4—V1—N2 91.3 (2) N2—C9—H9B 109.3
O1—V1—N2 165.2 (2) C8—C9—H9B 109.3
O3—V1—N2 98.79 (17) H9A—C9—H9B 108.0
N1—V1—N2 80.5 (2) N2—C10—H10A 109.5
O2—V1—N2 81.70 (17) N2—C10—H10B 109.5
C7—N1—C8 120.0 (5) H10A—C10—H10B 109.5
C7—N1—V1 126.5 (4) N2—C10—H10C 109.5
C8—N1—V1 113.3 (4) H10A—C10—H10C 109.5
C10—N2—C9 109.3 (5) H10B—C10—H10C 109.5
C10—N2—C11 106.6 (5) N2—C11—H11A 109.5
C9—N2—C11 110.2 (5) N2—C11—H11B 109.5
C10—N2—V1 114.5 (4) H11A—C11—H11B 109.5
C9—N2—V1 104.7 (3) N2—C11—H11C 109.5
C11—N2—V1 111.6 (4) H11A—C11—H11C 109.5
C1—O1—V1 131.1 (4) H11B—C11—H11C 109.5
C13—O2—V1 128.8 (4) C13—C12—H12A 109.5
C15—O3—V1 131.3 (4) C13—C12—H12B 109.5
O1—C1—C6 124.5 (5) H12A—C12—H12B 109.5
O1—C1—C2 118.7 (5) C13—C12—H12C 109.5
C6—C1—C2 116.7 (6) H12A—C12—H12C 109.5
C3—C2—C1 122.4 (6) H12B—C12—H12C 109.5
C3—C2—Br1 120.5 (5) O2—C13—C14 123.5 (6)
C1—C2—Br1 117.1 (5) O2—C13—C12 117.1 (6)
C2—C3—C4 119.7 (6) C14—C13—C12 119.3 (5)
C2—C3—H3 120.1 C15—C14—C13 124.5 (5)
C4—C3—H3 120.1 C15—C14—H14 117.7
C5—C4—C3 120.5 (6) C13—C14—H14 117.7
C5—C4—Cl1 120.0 (5) O3—C15—C14 125.1 (6)
C3—C4—Cl1 119.5 (6) O3—C15—C16 116.0 (6)
C4—C5—C6 120.6 (6) C14—C15—C16 118.9 (6)
C4—C5—H5 119.7 C15—C16—H16A 109.5
C6—C5—H5 119.7 C15—C16—H16B 109.5
C1—C6—C5 119.9 (6) H16A—C16—H16B 109.5
C1—C6—C7 122.7 (5) C15—C16—H16C 109.5
C5—C6—C7 117.4 (6) H16A—C16—H16C 109.5
N1—C7—C6 126.5 (6) H16B—C16—H16C 109.5
N1—C7—H7 116.7
Open in a new tab

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5858).

References

  1. Bruker (1998). SMART and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  2. Cornman, C. R., Kampf, J., Lah, M. S. & Pecoraro, V. L. (1992). Inorg. Chem. 31, 2035–2043.
  3. Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  4. Hiromura, M., Nakayama, A., Adachi, Y., Doi, M. & Sakurai, H. (2007). J. Biol. Inorg. Chem. 12, 1275–1287. [DOI] [PubMed]
  5. Kurup, M. R. P., Seena, E. B. & Kuriakose, M. (2010). Struct. Chem. 21, 599–605.
  6. Li, X., Lah, M. S. & Pecoraro, V. L. (1988). Inorg. Chem. 27, 4657–4664.
  7. Rosenthal, E. C. E., Cui, H. L. & Hummert, M. (2008). Inorg. Chem. Commun. 11, 918–920.
  8. Sarkar, A. & Pal, S. (2006). Polyhedron, 25, 1689–1694.
  9. Seena, E. B., Mathew, N., Kuriakose, M. & Kurup, M. R. P. (2008). Polyhedron, 27, 1455–1462.
  10. Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  11. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  12. Smith, T. S., Root, C. A., Kampf, J. W., Rasmussen, P. G. & Pecoraro, V. L. (2000). J. Am. Chem. Soc. 122, 767–775.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811015406/hb5858sup1.cif

e-67-0m650-sup1.cif (17.8KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811015406/hb5858Isup2.hkl

e-67-0m650-Isup2.hkl (189.4KB, hkl)

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

RESOURCES