(E)-3-Bromo-N′-(2,4-dichloro­benzyl­idene)benzohydrazide

Abstract

The title compound, C₁₄H₉BrCl₂N₂O, was synthesized by the reaction of 2,4-dichloro­benzaldehyde with an equimolar quantity of 3-bromo­benzohydrazide in methanol. The mol­ecule displays an E configuration about the C=N bond. The dihedral angle between the two benzene rings is 5.3 (2)°. In the crystal structure, mol­ecules are linked through inter­molecular N—H⋯O and C—H⋯O hydrogen bonds, forming chains running along the c axis.

Related literature

For the crystal structures of hydrazone compounds, see: Mohd Lair et al. (2009 ▶); Fun et al. (2008 ▶); Li & Ban (2009 ▶); Zhu et al. (2009 ▶); Yang (2007 ▶); You et al. (2008 ▶). For hydrazone compounds reported previously by our group, see: Qu et al. (2008 ▶); Yang et al. (2008 ▶); Cao & Lu (2009a ▶,b ▶); Qu & Cao (2009 ▶); Cao & Wang (2009 ▶); Cao (2009 ▶).

Experimental

Crystal data

• C₁₄H₉BrCl₂N₂O

• M _r = 372.04

• Monoclinic,

• a = 12.140 (2) Å

• b = 14.356 (3) Å

• c = 8.452 (2) Å

• β = 96.019 (3)°

• V = 1464.9 (5) ų

• Z = 4

• Mo Kα radiation

• μ = 3.17 mm⁻¹

• T = 298 K

• 0.20 × 0.20 × 0.18 mm

Data collection

• Bruker SMART CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2001 ▶) T _min = 0.570, T _max = 0.600 (expected range = 0.538–0.566)

• 6615 measured reflections

• 2350 independent reflections

• 1561 reflections with I > 2σ(I)

• R _int = 0.048

Refinement

• R[F ² > 2σ(F ²)] = 0.042

• wR(F ²) = 0.094

• S = 1.01

• 2350 reflections

• 184 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.64 e Å⁻³

• Δρ_min = −0.76 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1i	0.90 (1)	2.11 (3)	2.898 (4)	146 (4)
C7—H7⋯O1i	0.93	2.32	3.134 (5)	146

Symmetry code: (i) .

supplementary crystallographic information

Comment

Study on the crystal structures of hydrazone derivatives is a hot topic in structural chemistry. In the last few years, crystal structures of a large number of hydrazone compounds have been reported (Mohd Lair et al., 2009; Fun et al., 2008; Li & Ban, 2009; Zhu et al., 2009; Yang, 2007; You et al., 2008). As a continuation of our work in this area (Qu et al., 2008; Yang et al., 2008; Cao & Lu, 2009a,b; Qu & Cao, 2009; Cao & Wang, 2009), the title new hydrazone compound derived from the reaction of 2,4-dichlorobenzaldehyde with an equimolar quantity of 3-bromobenzohydrazide is reported.

In the title compound (Fig. 1), the dihedral angle between the two benzene rings is 5.3 (2)°. The molecule displays an E configuration about the C═N bond. In the crystal structure, molecules are linked through intermolecular N—H···O and C—H···O hydrogen bonds (Table 1) to form chains running along the c axis (Fig. 2).

Experimental

The title compound was prepared by refluxing equimolar quantities of 2,4-chlorobenzaldehyde with 3-bromobenzohydrazide in methanol. Colourless block-shaped crystals were formed by slow evaporation of the solution 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. The other H atoms were placed in idealized positions and constrained to ride on their parent atoms, with C-H distances of 0.93 Å, and with U_iso(H) set at 1.2U_eq(C).

Figures

Fig. 1.

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

Fig. 2.

The molecular packing of the title compound, viewed along the b axis. Hydrogen bonds are shown as dashed lines. C-bound H atoms have been omitted for clarity.

Crystal data

C14H9BrCl2N2O	F(000) = 736
Mr = 372.04	Dx = 1.687 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1215 reflections
a = 12.140 (2) Å	θ = 2.2–24.5°
b = 14.356 (3) Å	µ = 3.17 mm−1
c = 8.452 (2) Å	T = 298 K
β = 96.019 (3)°	Block, colourless
V = 1464.9 (5) Å3	0.20 × 0.20 × 0.18 mm
Z = 4

Data collection

Bruker SMART CCD area-detector diffractometer	2350 independent reflections
Radiation source: fine-focus sealed tube	1561 reflections with I > 2σ(I)
graphite	Rint = 0.048
ω scans	θmax = 24.2°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→13
Tmin = 0.570, Tmax = 0.600	k = −16→15
6615 measured reflections	l = −4→9

Refinement

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	w = 1/[σ2(Fo2) + (0.027P)2 + 1.2965P] where P = (Fo2 + 2Fc2)/3
2350 reflections	(Δ/σ)max = 0.001
184 parameters	Δρmax = 0.64 e Å−3
1 restraint	Δρmin = −0.76 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
Br1	0.63560 (5)	0.68952 (3)	0.11003 (7)	0.0796 (3)
Cl1	0.77292 (12)	−0.09489 (8)	0.12692 (16)	0.0724 (4)
Cl2	1.00210 (13)	−0.17858 (10)	−0.36215 (18)	0.0857 (5)
N1	0.7760 (3)	0.1874 (2)	−0.0336 (4)	0.0359 (8)
N2	0.7287 (3)	0.2522 (2)	0.0607 (4)	0.0371 (8)
O1	0.6990 (2)	0.34967 (18)	−0.1509 (3)	0.0505 (8)
C1	0.8471 (3)	0.0368 (3)	−0.0658 (5)	0.0376 (10)
C2	0.8405 (3)	−0.0571 (3)	−0.0332 (5)	0.0422 (10)
C3	0.8859 (4)	−0.1247 (3)	−0.1250 (6)	0.0494 (12)
H3	0.8792	−0.1877	−0.1025	0.059*
C4	0.9409 (4)	−0.0953 (3)	−0.2499 (6)	0.0511 (12)
C5	0.9513 (4)	−0.0029 (3)	−0.2835 (5)	0.0503 (12)
H5	0.9904	0.0157	−0.3670	0.060*
C6	0.9041 (3)	0.0622 (3)	−0.1940 (5)	0.0434 (11)
H6	0.9100	0.1249	−0.2192	0.052*
C7	0.7967 (3)	0.1081 (3)	0.0279 (5)	0.0380 (10)
H7	0.7803	0.0953	0.1307	0.046*
C8	0.6924 (3)	0.3329 (3)	−0.0095 (5)	0.0359 (10)
C9	0.6420 (3)	0.4015 (3)	0.0939 (4)	0.0339 (9)
C10	0.6578 (3)	0.4950 (3)	0.0618 (5)	0.0378 (10)
H10	0.7001	0.5125	−0.0188	0.045*
C11	0.6103 (4)	0.5617 (3)	0.1505 (5)	0.0471 (12)
C12	0.5449 (4)	0.5370 (3)	0.2661 (5)	0.0567 (13)
H12	0.5120	0.5826	0.3237	0.068*
C13	0.5282 (4)	0.4437 (4)	0.2965 (5)	0.0548 (13)
H13	0.4832	0.4266	0.3741	0.066*
C14	0.5781 (3)	0.3756 (3)	0.2123 (5)	0.0422 (11)
H14	0.5685	0.3129	0.2353	0.051*
H2	0.732 (4)	0.243 (3)	0.1660 (16)	0.080*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Br1	0.0888 (4)	0.0329 (3)	0.1108 (5)	0.0064 (3)	−0.0197 (3)	−0.0116 (3)
Cl1	0.0879 (10)	0.0444 (7)	0.0906 (10)	−0.0053 (7)	0.0363 (8)	0.0120 (7)
Cl2	0.0982 (11)	0.0673 (9)	0.0926 (10)	0.0235 (8)	0.0146 (9)	−0.0379 (8)
N1	0.048 (2)	0.0266 (18)	0.0342 (19)	0.0030 (16)	0.0087 (16)	−0.0037 (16)
N2	0.059 (2)	0.0253 (18)	0.0288 (18)	0.0078 (16)	0.0119 (18)	−0.0020 (16)
O1	0.084 (2)	0.0390 (17)	0.0310 (18)	0.0149 (15)	0.0173 (16)	0.0037 (13)
C1	0.041 (2)	0.034 (2)	0.037 (2)	0.0047 (19)	−0.001 (2)	−0.0054 (19)
C2	0.042 (3)	0.035 (2)	0.049 (3)	0.003 (2)	0.003 (2)	−0.003 (2)
C3	0.050 (3)	0.032 (2)	0.064 (3)	0.004 (2)	−0.003 (3)	−0.007 (2)
C4	0.047 (3)	0.049 (3)	0.056 (3)	0.015 (2)	−0.003 (2)	−0.022 (2)
C5	0.058 (3)	0.048 (3)	0.047 (3)	0.005 (2)	0.011 (2)	−0.010 (2)
C6	0.056 (3)	0.035 (2)	0.039 (3)	0.000 (2)	0.005 (2)	−0.001 (2)
C7	0.050 (3)	0.033 (2)	0.031 (2)	0.001 (2)	0.006 (2)	−0.0001 (19)
C8	0.043 (3)	0.029 (2)	0.036 (3)	−0.0030 (18)	0.007 (2)	−0.0020 (19)
C9	0.040 (2)	0.034 (2)	0.028 (2)	0.0036 (19)	0.0027 (19)	−0.0033 (18)
C10	0.041 (2)	0.032 (2)	0.039 (2)	0.0013 (19)	0.001 (2)	−0.003 (2)
C11	0.055 (3)	0.032 (2)	0.050 (3)	0.011 (2)	−0.013 (2)	−0.009 (2)
C12	0.066 (3)	0.060 (3)	0.043 (3)	0.030 (3)	0.001 (3)	−0.013 (3)
C13	0.050 (3)	0.077 (4)	0.039 (3)	0.019 (3)	0.012 (2)	0.000 (3)
C14	0.047 (3)	0.042 (2)	0.038 (3)	0.005 (2)	0.006 (2)	0.002 (2)

Geometric parameters (Å, °)

Br1—C11	1.897 (4)	C5—C6	1.365 (5)
Cl1—C2	1.741 (4)	C5—H5	0.93
Cl2—C4	1.740 (4)	C6—H6	0.93
N1—C7	1.265 (4)	C7—H7	0.93
N1—N2	1.388 (4)	C8—C9	1.489 (5)
N2—C8	1.354 (5)	C9—C14	1.380 (5)
N2—H2	0.897 (10)	C9—C10	1.386 (5)
O1—C8	1.230 (4)	C10—C11	1.380 (5)
C1—C2	1.380 (5)	C10—H10	0.93
C1—C6	1.394 (5)	C11—C12	1.369 (6)
C1—C7	1.467 (5)	C12—C13	1.382 (6)
C2—C3	1.391 (6)	C12—H12	0.93
C3—C4	1.374 (6)	C13—C14	1.386 (6)
C3—H3	0.93	C13—H13	0.93
C4—C5	1.365 (6)	C14—H14	0.93
C7—N1—N2	116.3 (3)	N1—C7—H7	120.6
C8—N2—N1	117.2 (3)	C1—C7—H7	120.6
C8—N2—H2	123 (3)	O1—C8—N2	122.8 (3)
N1—N2—H2	119 (3)	O1—C8—C9	120.9 (3)
C2—C1—C6	117.1 (4)	N2—C8—C9	116.3 (3)
C2—C1—C7	122.5 (4)	C14—C9—C10	120.2 (3)
C6—C1—C7	120.4 (4)	C14—C9—C8	123.0 (4)
C1—C2—C3	122.3 (4)	C10—C9—C8	116.8 (4)
C1—C2—Cl1	120.1 (3)	C11—C10—C9	119.5 (4)
C3—C2—Cl1	117.6 (3)	C11—C10—H10	120.3
C4—C3—C2	117.9 (4)	C9—C10—H10	120.3
C4—C3—H3	121.1	C12—C11—C10	121.0 (4)
C2—C3—H3	121.1	C12—C11—Br1	119.7 (3)
C5—C4—C3	121.4 (4)	C10—C11—Br1	119.3 (4)
C5—C4—Cl2	120.0 (4)	C11—C12—C13	119.4 (4)
C3—C4—Cl2	118.5 (4)	C11—C12—H12	120.3
C4—C5—C6	119.8 (4)	C13—C12—H12	120.3
C4—C5—H5	120.1	C12—C13—C14	120.6 (4)
C6—C5—H5	120.1	C12—C13—H13	119.7
C5—C6—C1	121.5 (4)	C14—C13—H13	119.7
C5—C6—H6	119.2	C9—C14—C13	119.4 (4)
C1—C6—H6	119.2	C9—C14—H14	120.3
N1—C7—C1	118.8 (4)	C13—C14—H14	120.3

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1i	0.90 (1)	2.11 (3)	2.898 (4)	146 (4)
C7—H7···O1i	0.93	2.32	3.134 (5)	146

Symmetry codes: (i) x, −y+1/2, z+1/2.