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Acta Cryst. (2009). E65, o508    [ doi:10.1107/S1600536809002165 ]

(E)-4-Bromo-N'-(2-nitrobenzylidene)benzohydrazide

M.-J. Zhang, L.-Z. Yin, D.-C. Wang, X.-M. Deng and J.-B. Liu

Abstract top

The title compound, C14H10BrN3O3, was obtained by a condensation reaction between 2-nitrobenzaldehyde and 4-bromobenzohydrazide. The dihedral angle between the two benzene rings is 4.1 (2)°. The molecule displays an E configuration about the C=N bond. In the crystal, molecules are linked into a chain along [100] by intermolecular N-H...O hydrogen bonds.

Comment top

Hydrazones and Schiff bases have attracted much attention for their excellent biological properties, especially for their potential pharmacological and antitumor properties (Kucukguzel et al., 2006; Khattab et al., 2005; Karthikeyan et al., 2006; Okabe et al., 1993). Recently, a large number of hydrazone derivatives have been prepared and structurally characterized (Shan et al., 2008; Fun et al., 2008; Ma et al., 2008; Diao et al., 2008a,b; Ejsmont et al., 2008). As part of the ongoing study, we report herein the crystal structure of the title compound.

The molecular structure of the title compound is shown in Fig. 1. The dihedral angle between the two benzene rings is 4.1 (2)°. The molecule of the compound displays an E configuration about the C═N bond. The bond values are typical (Allen et al., 1987). The molecules are linked into a chain along the [100] by intermolecular N—H···O hydrogen bonds.

Related literature top

For the biological properties of Schiff base and hydrazone compounds, see: Kucukguzel et al. (2006); Khattab et al. (2005); Karthikeyan et al. (2006); Okabe et al. (1993). For bond-length data, see: Allen et al. (1987). For related structures, see: Shan et al. (2008); Fun et al. (2008); Ma et al. (2008); Diao et al. (2008a,b); Ejsmont et al. (2008).

Experimental top

2-Nitrobenzaldehyde (1.0 mmol, 151.1 mg) was dissolved in methanol (50 ml) and then 4-bromobenzohydrazide (1.0 mmol, 215.0 mg) was added slowly into the solution, and the mixture was kept at reflux with continuous stirring for 1 h. After the solution had cooled to room temperature colourless crystals appeared. The crystals were filtered and washed with methanol for three times. Recrystallization from an absolute methanol yielded block-shaped single crystals of the title compound.

Refinement top

The amide H atom was located in a difference map and its positional parameters were refined. All other H atoms were placed in calculated positions (C-H = 0.93 Å) and refined using a riding model. The Uiso(H) values were set at 1.2Ueq(C,N).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (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 with 30% probability displacement ellipsoids for non-H atoms.
(E)-4-Bromo-N'-(2-nitrobenzylidene)benzohydrazide top
Crystal data top
C14H10BrN3O3Z = 1
Mr = 348.16F(000) = 174
Triclinic, P1Dx = 1.654 Mg m−3
Hall symbol: P 1Mo Kα radiation, λ = 0.71073 Å
a = 4.8718 (17) ÅCell parameters from 1163 reflections
b = 6.842 (2) Åθ = 2.8–26.3°
c = 10.709 (4) ŵ = 2.95 mm−1
α = 98.014 (5)°T = 298 K
β = 93.258 (6)°Block, colourless
γ = 97.413 (5)°0.20 × 0.18 × 0.17 mm
V = 349.5 (2) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		1998 independent reflections
Radiation source: fine-focus sealed tube1584 reflections with I > 2σ(I)
graphiteRint = 0.013
ω scansθmax = 30.7°, θmin = 1.9°
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		h = −6→6
Tmin = 0.590, Tmax = 0.634k = −8→8
2347 measured reflectionsl = −11→15
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064 w = 1/[σ2(Fo2) + (0.0058P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.95(Δ/σ)max = 0.001
1998 reflectionsΔρmax = 0.22 e Å−3
193 parametersΔρmin = −0.23 e Å−3
3 restraintsAbsolute structure: Flack (1983), 235 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.021 (8)
Crystal data top
C14H10BrN3O3γ = 97.413 (5)°
Mr = 348.16V = 349.5 (2) Å3
Triclinic, P1Z = 1
a = 4.8718 (17) ÅMo Kα radiation
b = 6.842 (2) ŵ = 2.95 mm−1
c = 10.709 (4) ÅT = 298 K
α = 98.014 (5)°0.20 × 0.18 × 0.17 mm
β = 93.258 (6)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		1998 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2001)		1584 reflections with I > 2σ(I)
Tmin = 0.590, Tmax = 0.634Rint = 0.013
2347 measured reflectionsθmax = 30.7°
Refinement top
R[F2 > 2σ(F2)] = 0.027H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.064Δρmax = 0.22 e Å−3
S = 0.95Δρmin = −0.23 e Å−3
1998 reflectionsAbsolute structure: Flack (1983), 235 Friedel pairs
193 parametersFlack parameter: 0.021 (8)
3 restraints
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
Br10.28524 (6)−0.18204 (5)−0.03061 (4)0.08281 (18)
O10.9938 (4)0.7003 (4)0.2644 (2)0.0599 (6)
O20.1064 (8)1.2188 (6)0.7780 (3)0.0860 (11)
O30.2286 (10)0.9674 (5)0.6631 (3)0.1064 (15)
N10.5685 (5)0.7559 (4)0.3185 (2)0.0399 (5)
H10.394 (9)0.725 (7)0.293 (4)0.048*
N20.6709 (5)0.9301 (4)0.3980 (2)0.0405 (5)
N30.2485 (7)1.1447 (5)0.6997 (3)0.0584 (8)
C10.6174 (7)0.4513 (5)0.1848 (3)0.0385 (7)
C20.7401 (7)0.3754 (5)0.0775 (3)0.0506 (8)
H20.89100.45050.04950.061*
C30.6386 (8)0.1890 (6)0.0126 (3)0.0564 (9)
H30.71800.1400−0.06020.068*
C40.4217 (8)0.0767 (5)0.0555 (3)0.0504 (8)
C50.2932 (7)0.1486 (5)0.1614 (3)0.0447 (7)
H50.14290.07220.18890.054*
C60.3932 (6)0.3357 (5)0.2250 (3)0.0420 (7)
H60.30900.38550.29620.050*
C70.7440 (6)0.6473 (4)0.2577 (3)0.0404 (6)
C80.4917 (6)1.0171 (4)0.4562 (3)0.0384 (6)
H80.30610.96090.44790.046*
C90.5831 (6)1.2100 (4)0.5376 (3)0.0393 (6)
C100.4633 (7)1.2766 (5)0.6481 (3)0.0433 (7)
C110.5462 (8)1.4635 (6)0.7158 (3)0.0607 (9)
H110.46341.50290.78960.073*
C120.7486 (9)1.5906 (6)0.6752 (4)0.0660 (10)
H120.80151.71780.71990.079*
C130.8755 (8)1.5290 (5)0.5668 (3)0.0550 (9)
H131.01721.61390.53970.066*
C140.7919 (8)1.3419 (6)0.4990 (3)0.0489 (9)
H140.87721.30310.42580.059*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Br10.1255 (4)0.04369 (19)0.0679 (2)−0.00267 (18)0.00284 (18)−0.01585 (13)
O10.0231 (11)0.0608 (15)0.0872 (15)−0.0003 (10)0.0026 (10)−0.0128 (12)
O20.082 (2)0.113 (3)0.074 (2)0.030 (2)0.0420 (17)0.0233 (19)
O30.149 (4)0.068 (3)0.087 (2)−0.047 (2)0.049 (2)−0.0006 (17)
N10.0237 (12)0.0358 (13)0.0545 (13)−0.0004 (10)−0.0015 (10)−0.0072 (11)
N20.0343 (13)0.0331 (12)0.0494 (12)−0.0022 (10)−0.0040 (10)−0.0015 (10)
N30.057 (2)0.068 (2)0.0476 (14)−0.0014 (16)0.0036 (14)0.0092 (14)
C10.0303 (16)0.0361 (15)0.0469 (15)0.0039 (13)−0.0061 (13)0.0027 (12)
C20.0450 (19)0.050 (2)0.0551 (17)0.0058 (15)0.0104 (14)0.0015 (15)
C30.067 (2)0.057 (2)0.0417 (15)0.0094 (18)0.0084 (15)−0.0075 (14)
C40.062 (2)0.0360 (16)0.0488 (16)0.0072 (15)−0.0087 (15)−0.0032 (13)
C50.0430 (18)0.0365 (16)0.0515 (16)−0.0015 (13)0.0030 (14)0.0024 (13)
C60.0379 (17)0.0418 (17)0.0438 (15)0.0048 (13)0.0031 (13)−0.0008 (13)
C70.0318 (16)0.0389 (16)0.0484 (14)0.0018 (12)−0.0009 (12)0.0038 (12)
C80.0322 (15)0.0356 (15)0.0435 (14)−0.0016 (13)0.0004 (12)−0.0006 (12)
C90.0385 (16)0.0325 (15)0.0444 (14)−0.0001 (12)−0.0029 (12)0.0039 (12)
C100.0401 (17)0.0418 (16)0.0464 (14)0.0022 (13)0.0033 (13)0.0042 (12)
C110.070 (2)0.053 (2)0.0542 (17)0.0114 (19)0.0013 (17)−0.0095 (15)
C120.079 (3)0.0351 (17)0.075 (2)−0.0046 (18)−0.004 (2)−0.0064 (16)
C130.058 (2)0.0404 (19)0.0614 (19)−0.0124 (15)0.0002 (17)0.0091 (15)
C140.0495 (18)0.041 (2)0.051 (2)−0.0091 (15)0.0001 (17)0.0075 (18)
Geometric parameters (Å, °) top
Br1—C41.897 (3)C4—C51.387 (5)
O1—C71.219 (4)C5—C61.377 (4)
O2—N31.216 (5)C5—H50.93
O3—N31.211 (5)C6—H60.93
N1—C71.341 (4)C8—C91.478 (4)
N1—N21.382 (3)C8—H80.93
N1—H10.87 (4)C9—C141.391 (5)
N2—C81.264 (4)C9—C101.395 (4)
N3—C101.474 (5)C10—C111.378 (4)
C1—C61.389 (5)C11—C121.360 (6)
C1—C21.393 (5)C11—H110.93
C1—C71.493 (4)C12—C131.386 (6)
C2—C31.380 (5)C12—H120.93
C2—H20.93C13—C141.380 (5)
C3—C41.364 (5)C13—H130.93
C3—H30.93C14—H140.93
C7—N1—N2119.9 (2)O1—C7—N1122.7 (3)
C7—N1—H1116 (3)O1—C7—C1121.2 (3)
N2—N1—H1123 (3)N1—C7—C1116.0 (2)
C8—N2—N1115.5 (2)N2—C8—C9118.6 (3)
O3—N3—O2123.8 (4)N2—C8—H8120.7
O3—N3—C10117.7 (3)C9—C8—H8120.7
O2—N3—C10118.5 (4)C14—C9—C10116.6 (3)
C6—C1—C2118.7 (3)C14—C9—C8118.6 (3)
C6—C1—C7122.3 (3)C10—C9—C8124.7 (3)
C2—C1—C7118.8 (3)C11—C10—C9121.9 (3)
C3—C2—C1120.2 (3)C11—C10—N3117.4 (3)
C3—C2—H2119.9C9—C10—N3120.7 (3)
C1—C2—H2119.9C12—C11—C10120.3 (3)
C4—C3—C2119.9 (3)C12—C11—H11119.8
C4—C3—H3120.1C10—C11—H11119.8
C2—C3—H3120.1C11—C12—C13119.5 (3)
C3—C4—C5121.3 (3)C11—C12—H12120.3
C3—C4—Br1120.4 (3)C13—C12—H12120.3
C5—C4—Br1118.3 (3)C14—C13—C12120.1 (3)
C6—C5—C4118.6 (3)C14—C13—H13119.9
C6—C5—H5120.7C12—C13—H13119.9
C4—C5—H5120.7C13—C14—C9121.5 (3)
C5—C6—C1121.3 (3)C13—C14—H14119.2
C5—C6—H6119.4C9—C14—H14119.2
C1—C6—H6119.4
C7—N1—N2—C8−176.5 (3)N2—C8—C9—C1436.5 (4)
C6—C1—C2—C30.3 (5)N2—C8—C9—C10−147.7 (3)
C7—C1—C2—C3175.9 (3)C14—C9—C10—C110.1 (4)
C1—C2—C3—C4−1.6 (5)C8—C9—C10—C11−175.8 (3)
C2—C3—C4—C52.2 (5)C14—C9—C10—N3−177.4 (3)
C2—C3—C4—Br1−178.6 (3)C8—C9—C10—N36.6 (4)
C3—C4—C5—C6−1.4 (5)O3—N3—C10—C11−160.0 (4)
Br1—C4—C5—C6179.4 (2)O2—N3—C10—C1118.4 (5)
C4—C5—C6—C10.1 (4)O3—N3—C10—C917.7 (5)
C2—C1—C6—C50.4 (4)O2—N3—C10—C9−163.9 (3)
C7—C1—C6—C5−175.0 (3)C9—C10—C11—C120.6 (5)
N2—N1—C7—O1−3.6 (4)N3—C10—C11—C12178.3 (4)
N2—N1—C7—C1173.8 (2)C10—C11—C12—C13−1.5 (6)
C6—C1—C7—O1143.2 (3)C11—C12—C13—C141.6 (6)
C2—C1—C7—O1−32.3 (4)C12—C13—C14—C9−0.8 (6)
C6—C1—C7—N1−34.3 (4)C10—C9—C14—C130.0 (5)
C2—C1—C7—N1150.3 (3)C8—C9—C14—C13176.1 (3)
N1—N2—C8—C9−176.7 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.900 (11)1.909 (19)2.791 (3)166 (6)
Symmetry codes: (i) x−1, y, z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.900 (11)1.909 (19)2.791 (3)166 (6)
Symmetry codes: (i) x−1, y, z.
references
References top

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