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

Cao, G.-B.

doi:10.1107/S1600536809030220

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2085

doi:10.1107/S1600536809030220

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

Guo-Biao Cao ^a ^*

^aDepartment of Chemistry, Ankang University, Ankang Shanxi 725000, People's Republic of China
^*Correspondence e-mail: guobiao_cao@126.com

(Received 29 July 2009; accepted 29 July 2009; online 8 August 2009)

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, P 2₁ /c
a = 12.140 (2) Å
b = 14.356 (3) Å
c = 8.452 (2) Å
β = 96.019 (3)°
V = 1464.9 (5) Å³
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[F² > 2σ(F²)] = 0.042
wR(F²) = 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

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) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030220/ci2871sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809030220/ci2871Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

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 top

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.

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

	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.

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

Crystal data top

C₁₄H₉BrCl₂N₂O	F(000) = 736
M_r = 372.04	D_x = 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 top

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

Refinement top

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(F_o²) + (0.027P)² + 1.2965P] where P = (F_o² + 2F_c²)/3
2350 reflections	(Δ/σ)_max = 0.001
184 parameters	Δρ_max = 0.64 e Å⁻³
1 restraint	Δρ_min = −0.76 e Å⁻³

Crystal data top

C₁₄H₉BrCl₂N₂O	V = 1464.9 (5) Å³
M_r = 372.04	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 12.140 (2) Å	µ = 3.17 mm⁻¹
b = 14.356 (3) Å	T = 298 K
c = 8.452 (2) Å	0.20 × 0.20 × 0.18 mm
β = 96.019 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2350 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1561 reflections with I > 2σ(I)
T_min = 0.570, T_max = 0.600	R_int = 0.048
6615 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	1 restraint
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.01	Δρ_max = 0.64 e Å⁻³
2350 reflections	Δρ_min = −0.76 e Å⁻³
184 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
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 (Å²) top

	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, º) top

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, º) top

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) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₉BrCl₂N₂O
M_r	372.04
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	12.140 (2), 14.356 (3), 8.452 (2)
β (°)	96.019 (3)
V (Å³)	1464.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.17
Crystal size (mm)	0.20 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.570, 0.600
No. of measured, independent and observed [I > 2σ(I)] reflections	6615, 2350, 1561
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.577

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.094, 1.01
No. of reflections	2350
No. of parameters	184
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.64, −0.76

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

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) x, −y+1/2, z+1/2.

Acknowledgements

The Vital Foundation of Ankang University (project No. 2008AKXY012) and the Special Scientific Research Foundation of the Education Office of Shanxi Province (Project No. 02 J K202) are gratefully acknowledged.

References

Bruker (2001). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Cao, G.-B. (2009). Acta Cryst. E65, o2086. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cao, G.-B. & Lu, X.-H. (2009a). Acta Cryst. E65, o1587. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cao, G.-B. & Lu, X.-H. (2009b). Acta Cryst. E65, o1600. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cao, G.-B. & Wang, X.-Y. (2009). Acta Cryst. E65, o1725. Web of Science CSD CrossRef IUCr Journals Google Scholar
Fun, H.-K., Patil, P. S., Rao, J. N., Kalluraya, B. & Chantrapromma, S. (2008). Acta Cryst. E64, o1707. Web of Science CSD CrossRef IUCr Journals Google Scholar
Li, C.-M. & Ban, H.-Y. (2009). Acta Cryst. E65, o1466. Web of Science CSD CrossRef IUCr Journals Google Scholar
Mohd Lair, N., Mohd Ali, H. & Ng, S. W. (2009). Acta Cryst. E65, o189. Web of Science CSD CrossRef IUCr Journals Google Scholar
Qu, L.-Z. & Cao, G.-B. (2009). Acta Cryst. E65, o1705. Web of Science CSD CrossRef IUCr Journals Google Scholar
Qu, L.-Z., Yang, T., Cao, G.-B. & Wang, X.-Y. (2008). Acta Cryst. E64, o2061. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, D.-S. (2007). J. Chem. Crystallogr. 37, 343–348. Web of Science CSD CrossRef CAS Google Scholar
Yang, T., Cao, G.-B., Xiang, J.-M. & Zhang, L.-H. (2008). Acta Cryst. E64, o1186. Web of Science CSD CrossRef IUCr Journals Google Scholar
You, Z.-L., Dai, W.-M., Xu, X.-Q. & Hu, Y.-Q. (2008). Pol. J. Chem. 82, 2215–2219. CAS Google Scholar
Zhu, C.-G., Wei, Y.-J. & Zhu, Q.-Y. (2009). Acta Cryst. E65, o85. Web of Science CSD CrossRef IUCr Journals Google Scholar