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Acta Cryst. (2009). E65, m718    [ doi:10.1107/S1600536809019928 ]

(4-Chlorobenzohydrazidato-[kappa]2N',O)[2-(4-chlorobenzoylhydrazono-[kappa]2N,O)propionato(2-)-[kappa]O]oxidovanadium(V)

H. W. Wong, K. M. Lo and S. W. Ng

Abstract top

In the crystal structure of the title compound, [VO(C7H6ClN2O)(C10H7ClN2O3)], the VV atom is N,O-chelated by the chlorobenzoylhydrazidate anion and O,N,O'-chelated by the (chlorobenzoylhydrazono)propionate dianion. The distorted octahedral trans-N2O4 coordination geometry is completed by the vanadyl O atom. In the crystal, molecules are linked by N-H...O hydrogen bonds into a linear chain parallel to [010].

Related literature top

For the analogous vanadyl complex without the chlorine substituent in the two ligands, see: Wong et al. (2009).

Experimental top

2-[p-Chlorobenzoylhydrazono]propionic acid was prepared from the condensation reaction of p-chlorobenzhydrazide and pyruvic acid. The compound (0.70 g, 3 mmol) and vanadyl sulfate (0.25 g, 1.5 mmol) in 20 ml of distilled water were heated for 5 h. Slow evaporation of the filtrate gave orange crystals.

Refinement top

Carbon-bound H-atoms were placed in calculated positions (C—H 0.95 to 0.98 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2 to 1.5U(C). The nitrogen-bound H-atoms were similarly treated (N–H 0.88 Å).

All phenylene rings were refined was rigid hexagons of 1.39 Å sides.

The final difference Fourier map had a large peak/deep hole in the vicnity of the V1 atom.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of VO(C7H6ClN2O)(C10H7ClN2O3) at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
(4-Chlorobenzohydrazidato-κ2N',O)[2-(4- chlorobenzoylhydrazono-κ2N,O)propionato(2-)- κO]oxidovanadium(V) top
Crystal data top
[V(C7H6ClN2O)(C10H7ClN2O3)O]F(000) = 1920
Mr = 475.15Dx = 1.704 Mg m−3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 957 reflections
a = 26.628 (2) Åθ = 2.5–23.1°
b = 5.7109 (3) ŵ = 0.86 mm−1
c = 24.772 (1) ÅT = 119 K
β = 100.396 (3)°Prism, orange
V = 3705.2 (4) Å30.40 × 0.04 × 0.04 mm
Z = 8
Data collection top
Bruker SMART APEX
diffractometer		4189 independent reflections
Radiation source: fine-focus sealed tube2154 reflections with I > 2σ(I)
graphiteRint = 0.174
ω scansθmax = 27.5°, θmin = 1.6°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −34→34
Tmin = 0.724, Tmax = 0.966k = −7→7
11303 measured reflectionsl = −32→30
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)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.175H-atom parameters constrained
S = 0.97 w = 1/[σ2(Fo2) + (0.0714P)2]
where P = (Fo2 + 2Fc2)/3
4189 reflections(Δ/σ)max = 0.001
239 parametersΔρmax = 1.40 e Å−3
0 restraintsΔρmin = −1.20 e Å−3
Crystal data top
[V(C7H6ClN2O)(C10H7ClN2O3)O]V = 3705.2 (4) Å3
Mr = 475.15Z = 8
Monoclinic, C2/cMo Kα radiation
a = 26.628 (2) ŵ = 0.86 mm−1
b = 5.7109 (3) ÅT = 119 K
c = 24.772 (1) Å0.40 × 0.04 × 0.04 mm
β = 100.396 (3)°
Data collection top
Bruker SMART APEX
diffractometer		4189 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2154 reflections with I > 2σ(I)
Tmin = 0.724, Tmax = 0.966Rint = 0.174
11303 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.059H-atom parameters constrained
wR(F2) = 0.175Δρmax = 1.40 e Å−3
S = 0.97Δρmin = −1.20 e Å−3
4189 reflectionsAbsolute structure: ?
239 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
V10.66692 (3)0.32434 (15)0.27882 (4)0.0216 (3)
Cl10.44158 (5)0.7483 (2)0.46938 (6)0.0289 (4)
Cl20.84139 (5)−0.6026 (2)0.53131 (6)0.0294 (4)
O10.67515 (13)0.1122 (6)0.21738 (17)0.0236 (9)
O20.63441 (13)−0.1245 (6)0.15164 (17)0.0281 (9)
O30.62899 (12)0.4195 (6)0.33748 (16)0.0237 (9)
O40.69433 (12)0.0349 (6)0.33560 (16)0.0222 (9)
O50.65919 (13)0.5607 (6)0.24415 (18)0.0296 (10)
N10.60013 (15)0.1326 (7)0.2650 (2)0.0203 (10)
N20.56469 (15)0.1678 (7)0.2986 (2)0.0236 (11)
N30.76603 (15)0.2341 (7)0.34041 (19)0.0206 (10)
H30.79900.25550.35160.025*
N40.73671 (15)0.3820 (7)0.3060 (2)0.0215 (10)
H40.75060.51060.29580.026*
C10.63701 (18)−0.0159 (9)0.1950 (3)0.0228 (12)
C20.59319 (18)−0.0213 (9)0.2266 (2)0.0225 (12)
C30.55037 (18)−0.1879 (9)0.2136 (3)0.0280 (14)
H3A0.5521−0.30160.24350.042*
H3B0.5526−0.27020.17940.042*
H3C0.5180−0.10250.20920.042*
C40.58356 (18)0.3289 (8)0.3341 (3)0.0221 (12)
C50.55047 (11)0.4234 (5)0.37140 (15)0.0196 (12)
C60.50488 (12)0.3112 (5)0.37506 (15)0.0239 (13)
H60.49650.16710.35650.029*
C70.47159 (10)0.4100 (5)0.40592 (17)0.0249 (13)
H7A0.44040.33330.40840.030*
C80.48390 (11)0.6209 (5)0.43310 (15)0.0227 (12)
C90.52949 (12)0.7331 (5)0.42944 (15)0.0239 (12)
H90.53790.87720.44800.029*
C100.56278 (10)0.6343 (5)0.39859 (16)0.0254 (13)
H100.59390.71100.39610.031*
C110.74052 (18)0.0506 (8)0.3562 (2)0.0186 (12)
C120.76740 (11)−0.1137 (5)0.39758 (13)0.0222 (13)
C130.73990 (8)−0.3013 (5)0.41306 (14)0.0245 (13)
H130.7054−0.32490.39580.029*
C140.76286 (11)−0.4543 (5)0.45377 (15)0.0241 (12)
H140.7441−0.58250.46440.029*
C150.81333 (11)−0.4198 (5)0.47899 (13)0.0251 (13)
C160.84083 (9)−0.2323 (6)0.46350 (14)0.0273 (13)
H160.8753−0.20870.48070.033*
C170.81787 (10)−0.0792 (5)0.42280 (15)0.0251 (13)
H170.83670.04890.41220.030*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
V10.0156 (4)0.0218 (5)0.0292 (7)0.0012 (4)0.0087 (4)0.0014 (4)
Cl10.0244 (6)0.0351 (8)0.0291 (9)0.0057 (5)0.0097 (6)−0.0082 (6)
Cl20.0273 (7)0.0282 (7)0.0332 (10)0.0029 (6)0.0066 (6)0.0046 (7)
O10.0189 (17)0.0246 (19)0.028 (2)0.0046 (15)0.0074 (17)0.0015 (17)
O20.0217 (18)0.040 (2)0.024 (3)0.0046 (17)0.0079 (17)−0.004 (2)
O30.0151 (16)0.0256 (19)0.031 (3)−0.0022 (14)0.0067 (17)−0.0060 (18)
O40.0150 (16)0.0225 (18)0.029 (3)−0.0032 (14)0.0048 (17)−0.0022 (17)
O50.0269 (19)0.025 (2)0.039 (3)0.0037 (16)0.013 (2)0.0060 (19)
N10.018 (2)0.019 (2)0.027 (3)0.0043 (17)0.011 (2)0.003 (2)
N20.018 (2)0.024 (2)0.032 (3)0.0009 (18)0.014 (2)−0.004 (2)
N30.0137 (19)0.025 (2)0.023 (3)0.0018 (17)0.0037 (18)0.005 (2)
N40.020 (2)0.018 (2)0.028 (3)−0.0018 (17)0.009 (2)0.000 (2)
C10.016 (2)0.020 (3)0.033 (4)0.003 (2)0.004 (2)−0.001 (3)
C20.016 (2)0.021 (3)0.030 (4)0.004 (2)0.004 (2)0.003 (3)
C30.018 (2)0.032 (3)0.036 (4)−0.004 (2)0.010 (3)−0.007 (3)
C40.018 (2)0.017 (2)0.032 (4)0.000 (2)0.005 (2)0.004 (3)
C50.019 (2)0.020 (3)0.021 (3)0.002 (2)0.006 (2)−0.003 (2)
C60.022 (2)0.021 (3)0.029 (4)−0.003 (2)0.006 (2)−0.007 (3)
C70.021 (3)0.021 (3)0.034 (4)0.000 (2)0.009 (3)−0.001 (3)
C80.022 (2)0.023 (3)0.023 (3)0.005 (2)0.006 (2)−0.004 (2)
C90.026 (3)0.026 (3)0.019 (3)0.000 (2)0.003 (2)−0.005 (2)
C100.017 (2)0.028 (3)0.033 (4)−0.001 (2)0.006 (2)−0.003 (3)
C110.017 (2)0.022 (3)0.017 (3)−0.003 (2)0.005 (2)−0.004 (2)
C120.019 (2)0.018 (3)0.031 (4)0.002 (2)0.011 (2)−0.008 (2)
C130.016 (2)0.024 (3)0.036 (4)−0.003 (2)0.011 (2)−0.006 (3)
C140.026 (3)0.024 (3)0.023 (3)−0.002 (2)0.006 (2)0.000 (3)
C150.023 (3)0.027 (3)0.027 (4)0.007 (2)0.009 (3)0.002 (3)
C160.014 (2)0.032 (3)0.035 (4)−0.001 (2)0.003 (2)0.003 (3)
C170.023 (3)0.024 (3)0.029 (4)−0.003 (2)0.007 (3)0.005 (3)
Geometric parameters (Å, °) top
V1—N12.064 (4)C3—H3C0.9800
V1—N41.888 (4)C4—C51.489 (5)
V1—O11.988 (4)C5—C61.3900
V1—O31.989 (3)C5—C101.3900
V1—O42.207 (4)C6—C71.3900
V1—O51.593 (4)C6—H60.9500
Cl1—C81.724 (2)C7—C81.3900
Cl2—C151.726 (3)C7—H7A0.9500
O1—C11.293 (6)C8—C91.3900
O2—C11.231 (6)C9—C101.3900
O3—C41.305 (5)C9—H90.9500
O4—C111.247 (6)C10—H100.9500
N1—C21.284 (7)C11—C121.476 (6)
N1—N21.381 (5)C12—C131.3900
N2—C41.308 (7)C12—C171.3900
N3—N41.344 (6)C13—C141.3900
N3—C111.345 (6)C13—H130.9500
N3—H30.8800C14—C151.3900
N4—H40.8800C14—H140.9500
C1—C21.518 (7)C15—C161.3900
C2—C31.475 (7)C16—C171.3900
C3—H3A0.9800C16—H160.9500
C3—H3B0.9800C17—H170.9500
O5—V1—N493.89 (19)O3—C4—C5117.5 (4)
O5—V1—O197.17 (18)N2—C4—C5118.3 (4)
N4—V1—O198.17 (16)C6—C5—C10120.0
O5—V1—O397.41 (17)C6—C5—C4119.7 (3)
N4—V1—O3106.77 (17)C10—C5—C4120.1 (3)
O1—V1—O3150.05 (14)C5—C6—C7120.0
O5—V1—N1109.67 (19)C5—C6—H6120.0
N4—V1—N1156.21 (18)C7—C6—H6120.0
O1—V1—N176.15 (15)C8—C7—C6120.0
O3—V1—N174.34 (15)C8—C7—H7A120.0
O5—V1—O4166.80 (18)C6—C7—H7A120.0
N4—V1—O473.27 (16)C9—C8—C7120.0
O1—V1—O487.83 (14)C9—C8—Cl1120.02 (18)
O3—V1—O483.82 (14)C7—C8—Cl1119.94 (18)
N1—V1—O483.36 (15)C10—C9—C8120.0
C1—O1—V1119.1 (3)C10—C9—H9120.0
C4—O3—V1115.6 (3)C8—C9—H9120.0
C11—O4—V1113.3 (3)C9—C10—C5120.0
C2—N1—N2121.6 (4)C9—C10—H10120.0
C2—N1—V1119.4 (3)C5—C10—H10120.0
N2—N1—V1119.0 (3)O4—C11—N3116.7 (5)
C4—N2—N1106.6 (4)O4—C11—C12123.9 (4)
N4—N3—C11114.1 (4)N3—C11—C12119.4 (4)
N4—N3—H3123.0C13—C12—C17120.0
C11—N3—H3123.0C13—C12—C11117.9 (3)
N3—N4—V1122.6 (3)C17—C12—C11122.0 (3)
N3—N4—H4118.7C12—C13—C14120.0
V1—N4—H4118.7C12—C13—H13120.0
O2—C1—O1125.1 (5)C14—C13—H13120.0
O2—C1—C2120.8 (5)C13—C14—C15120.0
O1—C1—C2114.1 (5)C13—C14—H14120.0
N1—C2—C3127.3 (5)C15—C14—H14120.0
N1—C2—C1110.3 (4)C16—C15—C14120.0
C3—C2—C1122.4 (5)C16—C15—Cl2119.67 (19)
C2—C3—H3A109.5C14—C15—Cl2120.29 (19)
C2—C3—H3B109.5C15—C16—C17120.0
H3A—C3—H3B109.5C15—C16—H16120.0
C2—C3—H3C109.5C17—C16—H16120.0
H3A—C3—H3C109.5C16—C17—C12120.0
H3B—C3—H3C109.5C16—C17—H17120.0
O3—C4—N2124.2 (5)C12—C17—H17120.0
O5—V1—O1—C1−101.5 (4)O1—C1—C2—N19.8 (6)
N4—V1—O1—C1163.5 (4)O2—C1—C2—C312.0 (8)
O3—V1—O1—C117.1 (6)O1—C1—C2—C3−169.0 (5)
N1—V1—O1—C17.1 (4)V1—O3—C4—N26.8 (7)
O4—V1—O1—C190.8 (4)V1—O3—C4—C5−170.4 (3)
O5—V1—O3—C4104.1 (4)N1—N2—C4—O3−4.5 (7)
N4—V1—O3—C4−159.6 (4)N1—N2—C4—C5172.6 (4)
O1—V1—O3—C4−14.5 (5)O3—C4—C5—C6−170.8 (4)
N1—V1—O3—C4−4.3 (4)N2—C4—C5—C611.9 (6)
O4—V1—O3—C4−89.1 (4)O3—C4—C5—C1015.1 (6)
O5—V1—O4—C11−14.2 (9)N2—C4—C5—C10−162.2 (4)
N4—V1—O4—C11−0.7 (3)C10—C5—C6—C70.0
O1—V1—O4—C1198.5 (3)C4—C5—C6—C7−174.2 (4)
O3—V1—O4—C11−110.3 (3)C5—C6—C7—C80.0
N1—V1—O4—C11174.8 (4)C6—C7—C8—C90.0
O5—V1—N1—C291.9 (4)C6—C7—C8—Cl1177.7 (3)
N4—V1—N1—C2−79.5 (6)C7—C8—C9—C100.0
O1—V1—N1—C2−0.8 (4)Cl1—C8—C9—C10−177.7 (3)
O3—V1—N1—C2−175.6 (4)C8—C9—C10—C50.0
O4—V1—N1—C2−90.2 (4)C6—C5—C10—C90.0
O5—V1—N1—N2−90.2 (4)C4—C5—C10—C9174.1 (4)
N4—V1—N1—N298.4 (5)V1—O4—C11—N3−1.1 (6)
O1—V1—N1—N2177.0 (4)V1—O4—C11—C12176.7 (3)
O3—V1—N1—N22.2 (3)N4—N3—C11—O43.1 (7)
O4—V1—N1—N287.6 (4)N4—N3—C11—C12−174.9 (4)
C2—N1—N2—C4178.1 (5)O4—C11—C12—C132.1 (6)
V1—N1—N2—C40.3 (5)N3—C11—C12—C13179.9 (3)
C11—N3—N4—V1−4.0 (6)O4—C11—C12—C17−174.7 (4)
O5—V1—N4—N3179.5 (4)N3—C11—C12—C173.1 (5)
O1—V1—N4—N3−82.7 (4)C17—C12—C13—C140.0
O3—V1—N4—N380.5 (4)C11—C12—C13—C14−176.9 (3)
N1—V1—N4—N3−8.6 (7)C12—C13—C14—C150.0
O4—V1—N4—N32.5 (4)C13—C14—C15—C160.0
V1—O1—C1—O2167.7 (4)C13—C14—C15—Cl2177.6 (3)
V1—O1—C1—C2−11.3 (6)C14—C15—C16—C170.0
N2—N1—C2—C3−3.4 (8)Cl2—C15—C16—C17−177.6 (3)
V1—N1—C2—C3174.5 (4)C15—C16—C17—C120.0
N2—N1—C2—C1177.9 (4)C13—C12—C17—C160.0
V1—N1—C2—C1−4.3 (6)C11—C12—C17—C16176.8 (3)
O2—C1—C2—N1−169.2 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O2i0.881.922.744 (5)156
N4—H4···O1i0.882.142.840 (5)136
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2.
Table 1
Selected geometric parameters (Å) top
V1—N12.064 (4)V1—O31.989 (3)
V1—N41.888 (4)V1—O42.207 (4)
V1—O11.988 (4)V1—O51.593 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3···O2i0.881.922.744 (5)156
N4—H4···O1i0.882.142.840 (5)136
Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2.
Acknowledgements top

We thank the University of Malaya (RG020/09AFR) for supporting this study.

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2008). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.

Wong, H. W., Lo, K. M. & Ng, S. W. (2009). Acta Cryst. E65, m422.