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Acta Crystallogr Sect E Struct Rep Online. 2008 November 1; 64(Pt 11): o2177.
Published online 2008 October 25. doi:  10.1107/S1600536808034107
PMCID: PMC2959696

(E)-N′-(2-Chloro-5-nitro­benzyl­idene)-4-methoxy­benzohydrazide

Abstract

In the title compound, C15H12ClN3O4, the benzohydrazide group is not planar and the mol­ecule exists in a trans configuration with respect to the methyl­idene unit. The dihedral angle between the two substituted benzene rings is 0.4 (3)°. In the crystal structure, mol­ecules are linked by inter­molecular N—H(...)O hydrogen bonds, forming chains parallel to the c axis.

Related literature

For the biological activity of hydrazones, see: Zhong et al. (2007 [triangle]); Raj et al. (2007 [triangle]); Jimenez-Pulido et al. (2008 [triangle]). For related structures, see: Yehye et al. (2008 [triangle]); Fun, Patil, Jebas et al. (2008 [triangle]); Yang et al. (2008 [triangle]); Ejsmont et al. (2008 [triangle]); Fun, Patil, Rao et al. (2008 [triangle]). For reference bond lengths, see: Allen et al. (1987 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-o2177-scheme1.jpg

Experimental

Crystal data

  • C15H12ClN3O4
  • M r = 333.73
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2177-efi1.jpg
  • a = 11.724 (2) Å
  • b = 13.482 (3) Å
  • c = 9.4259 (19) Å
  • β = 97.199 (3)°
  • V = 1478.1 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.28 mm−1
  • T = 298 (2) K
  • 0.20 × 0.20 × 0.17 mm

Data collection

  • Bruker SMART CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.946, T max = 0.953
  • 4284 measured reflections
  • 2735 independent reflections
  • 2320 reflections with I > 2σ(I)
  • R int = 0.015

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.089
  • S = 1.04
  • 2735 reflections
  • 212 parameters
  • 3 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.14 e Å−3
  • Δρmin = −0.19 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1079 Friedel pairs
  • Flack parameter: −0.01 (7)

Data collection: SMART (Bruker, 1998 [triangle]); cell refinement: SAINT (Bruker, 1998 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808034107/rz2255sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808034107/rz2255Isup2.hkl

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

Acknowledgments

Financial support of this work was provided by the Research Foundation of Liaoning Province (project No. 2008470).

supplementary crystallographic information

Comment

Hydrazones derived from the condensation of aldehydes with hydrazides have been demonstrated to possess excellent biological activities (Zhong et al., 2007; Raj et al., 2007; Jimenez-Pulido et al., 2008). Due to the easy synthesis of such compounds, a great deal of hydrazones have been synthesized and structurally characterized (Yehye et al., 2008; Fun, Patil, Jebas et al., 2008; Yang et al., 2008; Ejsmont et al., 2008). We report herein the crytal structure of the title new hydrazone compound.

In the structure of the title compound (Fig. 1), the molecule exists in a trans configuration with respect to the methylidene unit. The dihedral angle between the two substituted benzene rings is 0.4 (3)°. In the 2-chloro-5-nitrophenyl unit, the nitro group is slightly twisted from the mean plane of the C1–C6 ring with a dihedral angle of 7.4 (3)°. The same pattern can ben observed in a similar hydrazone compound (Fun, Patil, Rao et al., 2008). In the 4-methoxyphenyl unit, the methoxy group is nearly coplanar with the mean plane of the C9–C14 ring, with atom C15 deviating from the C9–C14 ring by 0.098 (2) Å. The C7-N1-N2-C8 torsion angle is 7.3 (3)°. The bond distances and angles are in normal ranges (Allen et al., 1987).

In the crystal structure, molecules are linked by intermolecular N—H···O hydrogen bonds (Table 1), to form chains parallel to the c axis (Fig. 2).

Experimental

The compound was prepared by refluxing 2-chloro-5-nitrobenzaldehyde (1.0 mol) with 4-methoxybenzohydrazide (1.0 mol) in methanol (100 ml). Excess methanol was removed from the mixture by distillation. The colourless solid product was filtered, and washed three times with methanol. Colourless block crystals of the title compound were obtained from a methanol solution by slow evaporation in air.

Refinement

Atom H2 was located in a difference Fourier map and refined isotropically, with the N–H distance restrained to 0.90 (1) Å. Other H atoms were placed in calculated positions (C—H = 0.93-0.96 Å) and refined as riding with Uiso(H) = 1.2 Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating group model was used for the methyl group.

Figures

Fig. 1.
The molecular structure of the title compound, showing 30% probability displacement ellipsoids for the non-hydrogen atoms.
Fig. 2.
Packing diagram of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines. Hydrogen atoms not involved in hydrogen bonds are omitted for clarity.

Crystal data

C15H12ClN3O4F(000) = 688
Mr = 333.73Dx = 1.500 Mg m3
Monoclinic, CcMo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2ycCell parameters from 1899 reflections
a = 11.724 (2) Åθ = 2.7–26.0°
b = 13.482 (3) ŵ = 0.28 mm1
c = 9.4259 (19) ÅT = 298 K
β = 97.199 (3)°Block, colourless
V = 1478.1 (5) Å30.20 × 0.20 × 0.17 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer2735 independent reflections
Radiation source: fine-focus sealed tube2320 reflections with I > 2σ(I)
graphiteRint = 0.015
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −12→15
Tmin = 0.946, Tmax = 0.953k = −17→14
4284 measured reflectionsl = −12→11

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090w = 1/[σ2(Fo2) + (0.0432P)2 + 0.2836P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
2735 reflectionsΔρmax = 0.14 e Å3
212 parametersΔρmin = −0.19 e Å3
3 restraintsAbsolute structure: Flack (1983), 1079 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.01 (7)

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.

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

xyzUiso*/Ueq
Cl10.12621 (9)0.12406 (5)0.37773 (10)0.0861 (3)
N10.13488 (17)0.41377 (14)0.18463 (19)0.0474 (5)
N20.09570 (18)0.49328 (13)0.2558 (2)0.0477 (4)
N30.3330 (2)0.2029 (2)−0.1503 (3)0.0806 (8)
O10.07475 (18)0.58146 (13)0.05053 (18)0.0603 (5)
O2−0.0721 (2)0.92744 (16)0.4294 (3)0.0838 (7)
O30.3489 (3)0.2876 (2)−0.1823 (3)0.1312 (12)
O40.3571 (2)0.1320 (2)−0.2230 (3)0.1006 (8)
C10.1933 (2)0.24746 (17)0.1773 (2)0.0466 (5)
C20.1870 (2)0.15042 (18)0.2246 (3)0.0521 (6)
C30.2269 (2)0.07102 (18)0.1509 (3)0.0625 (7)
H30.22110.00670.18480.075*
C40.2750 (2)0.0880 (2)0.0280 (3)0.0626 (7)
H40.30190.0356−0.02270.075*
C50.2829 (2)0.1836 (2)−0.0190 (3)0.0574 (7)
C60.2439 (2)0.26332 (17)0.0522 (3)0.0506 (6)
H60.25110.32730.01760.061*
C70.1489 (2)0.33260 (16)0.2508 (2)0.0478 (5)
H70.13150.32670.34400.057*
C80.06846 (19)0.57703 (16)0.1789 (2)0.0437 (5)
C90.0312 (2)0.66442 (16)0.2574 (2)0.0432 (5)
C10−0.0184 (2)0.66089 (17)0.3825 (2)0.0466 (5)
H10−0.02770.60010.42620.056*
C11−0.0548 (2)0.7478 (2)0.4443 (3)0.0536 (6)
H11−0.08900.74490.52800.064*
C12−0.0394 (2)0.83779 (18)0.3803 (3)0.0594 (7)
C130.0120 (3)0.8419 (2)0.2577 (3)0.0664 (7)
H130.02430.90310.21660.080*
C140.0454 (2)0.75687 (18)0.1949 (3)0.0576 (7)
H140.07780.76070.10990.069*
C15−0.1293 (3)0.9299 (3)0.5519 (5)0.0924 (11)
H15A−0.19780.89040.53590.139*
H15B−0.14930.99720.57140.139*
H15C−0.07960.90390.63200.139*
H20.085 (2)0.490 (2)0.3482 (13)0.080*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.1402 (7)0.0565 (4)0.0680 (4)0.0130 (5)0.0377 (4)0.0108 (4)
N10.0625 (12)0.0416 (10)0.0391 (10)0.0010 (8)0.0102 (9)−0.0058 (8)
N20.0704 (12)0.0389 (9)0.0353 (9)0.0033 (8)0.0128 (9)−0.0020 (7)
N30.0738 (16)0.094 (2)0.0798 (18)−0.0181 (14)0.0314 (13)−0.0263 (16)
O10.0928 (13)0.0558 (9)0.0343 (9)0.0018 (9)0.0157 (8)0.0020 (7)
O20.0947 (15)0.0526 (12)0.1063 (18)0.0148 (10)0.0216 (13)−0.0121 (11)
O30.187 (3)0.098 (2)0.131 (2)−0.042 (2)0.109 (2)−0.0274 (17)
O40.1071 (17)0.1107 (19)0.0928 (16)−0.0112 (14)0.0478 (14)−0.0467 (14)
C10.0483 (12)0.0468 (12)0.0440 (13)−0.0013 (10)0.0028 (10)−0.0074 (10)
C20.0607 (15)0.0487 (12)0.0455 (13)0.0046 (11)0.0015 (11)−0.0052 (10)
C30.0749 (17)0.0441 (13)0.0663 (18)0.0083 (12)0.0008 (14)−0.0078 (12)
C40.0590 (15)0.0581 (15)0.0696 (18)0.0076 (12)0.0029 (13)−0.0235 (13)
C50.0464 (14)0.0688 (17)0.0574 (15)−0.0061 (11)0.0080 (12)−0.0217 (13)
C60.0500 (13)0.0504 (13)0.0517 (14)−0.0037 (12)0.0071 (11)−0.0082 (11)
C70.0631 (14)0.0425 (12)0.0379 (12)−0.0009 (11)0.0067 (10)−0.0031 (9)
C80.0553 (13)0.0426 (11)0.0339 (11)−0.0066 (10)0.0085 (9)0.0000 (9)
C90.0510 (13)0.0428 (11)0.0352 (11)0.0004 (10)0.0028 (10)−0.0001 (9)
C100.0563 (14)0.0431 (12)0.0399 (12)−0.0016 (10)0.0046 (11)0.0018 (10)
C110.0512 (13)0.0615 (16)0.0481 (15)0.0030 (12)0.0064 (12)−0.0111 (11)
C120.0589 (15)0.0406 (13)0.0752 (19)0.0073 (11)−0.0051 (14)−0.0043 (12)
C130.0841 (19)0.0430 (13)0.0721 (18)0.0036 (13)0.0099 (15)0.0094 (13)
C140.0753 (17)0.0485 (14)0.0507 (14)−0.0021 (12)0.0144 (13)0.0100 (11)
C150.077 (2)0.081 (2)0.121 (3)0.0114 (16)0.017 (2)−0.038 (2)

Geometric parameters (Å, °)

Cl1—C21.725 (3)C4—H40.9300
N1—C71.260 (3)C5—C61.376 (3)
N1—N21.374 (2)C6—H60.9300
N2—C81.358 (3)C7—H70.9300
N2—H20.897 (10)C8—C91.485 (3)
N3—O31.202 (4)C9—C101.379 (3)
N3—O41.229 (3)C9—C141.397 (3)
N3—C51.458 (4)C10—C111.399 (3)
O1—C81.223 (3)C10—H100.9300
O2—C121.366 (3)C11—C121.376 (4)
O2—C151.406 (4)C11—H110.9300
C1—C21.387 (3)C12—C131.370 (4)
C1—C61.402 (3)C13—C141.370 (4)
C1—C71.469 (3)C13—H130.9300
C2—C31.389 (3)C14—H140.9300
C3—C41.370 (4)C15—H15A0.9600
C3—H30.9300C15—H15B0.9600
C4—C51.369 (4)C15—H15C0.9600
C7—N1—N2117.83 (18)C1—C7—H7120.8
C8—N2—N1117.34 (17)O1—C8—N2121.9 (2)
C8—N2—H2120.9 (19)O1—C8—C9120.8 (2)
N1—N2—H2121.7 (19)N2—C8—C9117.29 (18)
O3—N3—O4123.0 (3)C10—C9—C14118.4 (2)
O3—N3—C5118.3 (3)C10—C9—C8125.4 (2)
O4—N3—C5118.7 (3)C14—C9—C8116.1 (2)
C12—O2—C15118.8 (3)C9—C10—C11120.7 (2)
C2—C1—C6117.3 (2)C9—C10—H10119.7
C2—C1—C7123.4 (2)C11—C10—H10119.7
C6—C1—C7119.3 (2)C12—C11—C10119.5 (2)
C1—C2—C3122.1 (3)C12—C11—H11120.3
C1—C2—Cl1120.45 (19)C10—C11—H11120.3
C3—C2—Cl1117.4 (2)O2—C12—C13114.9 (3)
C4—C3—C2119.6 (3)O2—C12—C11125.0 (3)
C4—C3—H3120.2C13—C12—C11120.1 (2)
C2—C3—H3120.2C14—C13—C12120.7 (2)
C5—C4—C3118.9 (2)C14—C13—H13119.7
C5—C4—H4120.6C12—C13—H13119.7
C3—C4—H4120.6C13—C14—C9120.6 (2)
C4—C5—C6122.5 (3)C13—C14—H14119.7
C4—C5—N3119.5 (2)C9—C14—H14119.7
C6—C5—N3118.0 (3)O2—C15—H15A109.5
C5—C6—C1119.6 (2)O2—C15—H15B109.5
C5—C6—H6120.2H15A—C15—H15B109.5
C1—C6—H6120.2O2—C15—H15C109.5
N1—C7—C1118.5 (2)H15A—C15—H15C109.5
N1—C7—H7120.8H15B—C15—H15C109.5

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···O1i0.90 (1)2.15 (2)2.994 (3)156 (3)

Symmetry codes: (i) x, −y+1, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2255).

References

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