(E)-4-Bromo-N′-(2-chloro­benzyl­idene)benzohydrazide

Shu, X.-H.; Diao, Y.-P.; Li, M.-L.; Yan, X.; Liu, J.

doi:10.1107/S1600536809012860

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1034

doi:10.1107/S1600536809012860

Open

access

(E)-4-Bromo-N′-(2-chlorobenzylidene)benzohydrazide

Xiao-Hong Shu,^a Yun-Peng Diao,^a Mo-Lin Li,^b Xu Yan ^a and Jia Liu ^b ^*

^aCollege of Pharmacy, Dalian Medical University, Liaoning 116044, People's Republic of China, and ^bCollege of Basic Medical Sciences, Dalian Medical University, Liaoning 116044, People's Republic of China
^*Correspondence e-mail: jialiu09@126.com

(Received 4 April 2009; accepted 4 April 2009; online 18 April 2009)

In the title compound, C₁₄H₁₀BrClN₂O, the dihedral angle between the two benzene rings is 11.4 (2)°. In the crystal structure, molecules are connected via intermolecular N—H⋯O hydrogen bonds into one-dimensional chains running parallel to the c axis.

Related literature

For the biological activity of hydrazones and Schiff bases, see: Bhandari et al. (2008 ); Sinha et al. (2008 ). For a related structure, see: Pan & Yang (2005 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₄H₁₀BrClN₂O
M_r = 337.60
Monoclinic, P 2₁ /c
a = 11.218 (4) Å
b = 13.512 (5) Å
c = 9.200 (3) Å
β = 97.077 (6)°
V = 1383.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 3.16 mm⁻¹
T = 298 K
0.23 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Siemens, 1996 ) T_min = 0.491, T_max = 0.531
6907 measured reflections
2438 independent reflections
1948 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.035
wR(F²) = 0.094
S = 1.03
2438 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1ⁱ	0.86	2.12	2.918 (3)	154
Symmetry code: (i) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809012860/hb2944sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809012860/hb2944Isup2.hkl

checkCIF report

Comment top

Hydrazones and Schiff bases have attracted much attention for their excellent biological properties, especially for their potential pharmacological and antitumor properties (Bhandari et al., 2008; Sinha et al., 2008). In this paper, the crystal structure of the title compound, (I), a new Schiff base compound derived from the condensation reaction of 2-chlorobenzaldehyde with 4-bromobenzohydrazide is reported.

The Schiff base molecule of the compound displays a trans configuration with respect to the C=N and C—N bonds (Fig. 1). All the bond lengths are within normal ranges (Allen et al., 1987), and are comparable to those in the related compound N'-(2-chlorobenzylidene)-2-hydroxybenzohydrazide (Pan & Yang, 2005). The dihedral angle between the two benzene rings is 11.4 (2)°. In the crystal structure, the C₁₄H₁₀BrClN₂O molecules are connected via intermolecular N—H···O hydrogen bonds into one-dimensional chains running parallel to the c axis (Table 1 & Fig. 2).

Related literature top

For the biological activity of hydrazones and Schiff bases, see: Bhandari et al. (2008); Sinha et al. (2008). For a related structure, see: Pan & Yang (2005). For bond-length data, see: Allen et al. (1987).

Experimental top

2-Chlorobenzaldehyde (0.1 mmol) and 4-bromobenzohydrazide acid hydrazide (0.1 mmol) were dissolved in a 95% ethanol solution (10 ml). The mixture was stirred at room temperature to give a clear colorless solution. Colourless blocks of (I) were formed by gradual evaporation of the solvent over a period of five days at room temperature.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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 (I), with displacement ellipsoids drawn at the 30% probability level.
	Fig. 2. The one-dimensional chains structure along c axis. The donor···acceptor for the intermolecular hydrogen bonds are shown as dashed lines.

(E)-4-Bromo-N'-(2-chlorobenzylidene)benzohydrazide top

Crystal data top

C₁₄H₁₀BrClN₂O	F(000) = 672
M_r = 337.60	D_x = 1.620 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2695 reflections
a = 11.218 (4) Å	θ = 2.4–26.2°
b = 13.512 (5) Å	µ = 3.16 mm⁻¹
c = 9.200 (3) Å	T = 298 K
β = 97.077 (6)°	Block, colorless
V = 1383.9 (8) Å³	0.23 × 0.20 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2438 independent reflections
Radiation source: fine-focus sealed tube	1948 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω scans	θ_max = 25.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Siemens, 1996)	h = −13→13
T_min = 0.491, T_max = 0.531	k = −10→16
6907 measured reflections	l = −10→10

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)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0447P)² + 0.9326P] where P = (F_o² + 2F_c²)/3
2438 reflections	(Δ/σ)_max = 0.001
172 parameters	Δρ_max = 0.57 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₄H₁₀BrClN₂O	V = 1383.9 (8) Å³
M_r = 337.60	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.218 (4) Å	µ = 3.16 mm⁻¹
b = 13.512 (5) Å	T = 298 K
c = 9.200 (3) Å	0.23 × 0.20 × 0.20 mm
β = 97.077 (6)°

Data collection top

Bruker SMART CCD diffractometer	2438 independent reflections
Absorption correction: multi-scan (SADABS; Siemens, 1996)	1948 reflections with I > 2σ(I)
T_min = 0.491, T_max = 0.531	R_int = 0.023
6907 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.035	0 restraints
wR(F²) = 0.094	H-atom parameters constrained
S = 1.03	Δρ_max = 0.57 e Å⁻³
2438 reflections	Δρ_min = −0.39 e Å⁻³
172 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.45713 (4)	1.17921 (3)	0.84354 (5)	0.07653 (18)
Cl1	0.23484 (10)	0.37589 (7)	0.63350 (10)	0.0790 (3)
N1	0.1872 (2)	0.66418 (16)	0.4378 (2)	0.0423 (5)
N2	0.2302 (2)	0.74288 (16)	0.5254 (2)	0.0419 (5)
H2	0.2331	0.7398	0.6191	0.050*
O1	0.2623 (2)	0.83236 (15)	0.3250 (2)	0.0555 (6)
C1	0.1301 (3)	0.4950 (2)	0.4158 (3)	0.0439 (7)
C2	0.1495 (3)	0.3987 (2)	0.4655 (3)	0.0521 (7)
C3	0.1046 (3)	0.3167 (2)	0.3829 (4)	0.0634 (9)
H3	0.1184	0.2529	0.4190	0.076*
C4	0.0401 (3)	0.3319 (3)	0.2483 (4)	0.0674 (10)
H4	0.0100	0.2781	0.1924	0.081*
C5	0.0197 (3)	0.4264 (3)	0.1954 (4)	0.0670 (10)
H5	−0.0245	0.4358	0.1041	0.080*
C6	0.0637 (3)	0.5072 (3)	0.2759 (4)	0.0558 (8)
H6	0.0497	0.5705	0.2378	0.067*
C7	0.1768 (3)	0.5816 (2)	0.5014 (3)	0.0448 (7)
H7	0.1987	0.5760	0.6019	0.054*
C8	0.2680 (3)	0.82507 (19)	0.4591 (3)	0.0402 (6)
C9	0.3160 (2)	0.90782 (19)	0.5568 (3)	0.0387 (6)
C10	0.3159 (3)	1.0028 (2)	0.4976 (4)	0.0639 (10)
H10	0.2873	1.0121	0.3993	0.077*
C11	0.3572 (4)	1.0832 (2)	0.5811 (4)	0.0687 (10)
H11	0.3549	1.1463	0.5404	0.082*
C12	0.4020 (3)	1.0687 (2)	0.7257 (3)	0.0485 (7)
C13	0.4055 (3)	0.9757 (2)	0.7869 (3)	0.0502 (7)
H13	0.4371	0.9667	0.8844	0.060*
C14	0.3620 (3)	0.8957 (2)	0.7029 (3)	0.0432 (6)
H14	0.3635	0.8330	0.7447	0.052*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0834 (3)	0.0523 (2)	0.0923 (3)	−0.02495 (18)	0.0047 (2)	−0.02263 (19)
Cl1	0.1214 (8)	0.0504 (5)	0.0598 (6)	0.0029 (5)	−0.0099 (5)	0.0011 (4)
N1	0.0549 (14)	0.0366 (13)	0.0344 (12)	0.0020 (10)	0.0014 (10)	−0.0050 (10)
N2	0.0650 (15)	0.0336 (12)	0.0262 (11)	−0.0013 (10)	0.0018 (10)	−0.0021 (9)
O1	0.0959 (17)	0.0437 (12)	0.0263 (11)	0.0018 (11)	0.0054 (10)	0.0010 (8)
C1	0.0496 (16)	0.0391 (15)	0.0445 (16)	−0.0057 (12)	0.0120 (13)	−0.0079 (13)
C2	0.0590 (19)	0.0442 (17)	0.0542 (18)	−0.0014 (14)	0.0108 (15)	−0.0081 (14)
C3	0.076 (2)	0.0392 (17)	0.077 (3)	−0.0050 (15)	0.017 (2)	−0.0117 (16)
C4	0.076 (2)	0.058 (2)	0.066 (2)	−0.0167 (18)	0.0048 (19)	−0.0232 (18)
C5	0.069 (2)	0.071 (2)	0.058 (2)	−0.0143 (18)	−0.0046 (17)	−0.0136 (18)
C6	0.0590 (19)	0.0543 (19)	0.0540 (19)	−0.0083 (15)	0.0061 (15)	−0.0098 (15)
C7	0.0588 (18)	0.0397 (16)	0.0360 (15)	−0.0021 (13)	0.0058 (13)	−0.0027 (12)
C8	0.0519 (17)	0.0352 (14)	0.0332 (15)	0.0075 (12)	0.0038 (12)	0.0004 (11)
C9	0.0510 (16)	0.0333 (14)	0.0322 (14)	0.0015 (12)	0.0067 (12)	−0.0004 (11)
C10	0.105 (3)	0.0416 (17)	0.0414 (18)	−0.0093 (17)	−0.0061 (17)	0.0104 (14)
C11	0.103 (3)	0.0325 (17)	0.068 (2)	−0.0132 (17)	0.001 (2)	0.0098 (16)
C12	0.0519 (17)	0.0397 (16)	0.0542 (19)	−0.0110 (13)	0.0078 (14)	−0.0071 (14)
C13	0.0638 (19)	0.0464 (17)	0.0384 (16)	−0.0065 (14)	−0.0024 (14)	−0.0024 (13)
C14	0.0570 (17)	0.0341 (14)	0.0381 (15)	−0.0007 (12)	0.0042 (12)	0.0041 (12)

Geometric parameters (Å, º) top

Br1—C12	1.903 (3)	C5—C6	1.377 (4)
Cl1—C2	1.742 (3)	C5—H5	0.9300
N1—C7	1.272 (4)	C6—H6	0.9300
N1—N2	1.385 (3)	C7—H7	0.9300
N2—C8	1.359 (3)	C8—C9	1.493 (4)
N2—H2	0.8600	C9—C14	1.388 (4)
O1—C8	1.232 (3)	C9—C10	1.394 (4)
C1—C2	1.388 (4)	C10—C11	1.378 (5)
C1—C6	1.415 (4)	C10—H10	0.9300
C1—C7	1.470 (4)	C11—C12	1.377 (5)
C2—C3	1.401 (4)	C11—H11	0.9300
C3—C4	1.371 (5)	C12—C13	1.376 (4)
C3—H3	0.9300	C13—C14	1.383 (4)
C4—C5	1.375 (5)	C13—H13	0.9300
C4—H4	0.9300	C14—H14	0.9300

C7—N1—N2	116.8 (2)	N1—C7—H7	120.1
C8—N2—N1	118.2 (2)	C1—C7—H7	120.1
C8—N2—H2	120.9	O1—C8—N2	122.3 (3)
N1—N2—H2	120.9	O1—C8—C9	120.9 (2)
C2—C1—C6	116.9 (3)	N2—C8—C9	116.8 (2)
C2—C1—C7	122.6 (3)	C14—C9—C10	117.9 (3)
C6—C1—C7	120.5 (3)	C14—C9—C8	123.9 (2)
C1—C2—C3	122.1 (3)	C10—C9—C8	118.1 (2)
C1—C2—Cl1	120.3 (2)	C11—C10—C9	121.6 (3)
C3—C2—Cl1	117.5 (3)	C11—C10—H10	119.2
C4—C3—C2	119.1 (3)	C9—C10—H10	119.2
C4—C3—H3	120.5	C12—C11—C10	118.9 (3)
C2—C3—H3	120.5	C12—C11—H11	120.5
C3—C4—C5	120.3 (3)	C10—C11—H11	120.5
C3—C4—H4	119.8	C13—C12—C11	121.0 (3)
C5—C4—H4	119.8	C13—C12—Br1	119.5 (2)
C4—C5—C6	120.9 (3)	C11—C12—Br1	119.5 (2)
C4—C5—H5	119.5	C12—C13—C14	119.6 (3)
C6—C5—H5	119.5	C12—C13—H13	120.2
C5—C6—C1	120.7 (3)	C14—C13—H13	120.2
C5—C6—H6	119.7	C13—C14—C9	120.9 (3)
C1—C6—H6	119.7	C13—C14—H14	119.6
N1—C7—C1	119.9 (3)	C9—C14—H14	119.6

C7—N1—N2—C8	165.4 (3)	N1—N2—C8—C9	−178.9 (2)
C6—C1—C2—C3	−0.9 (5)	O1—C8—C9—C14	−157.9 (3)
C7—C1—C2—C3	180.0 (3)	N2—C8—C9—C14	22.8 (4)
C6—C1—C2—Cl1	177.7 (2)	O1—C8—C9—C10	21.4 (4)
C7—C1—C2—Cl1	−1.4 (4)	N2—C8—C9—C10	−158.0 (3)
C1—C2—C3—C4	0.5 (5)	C14—C9—C10—C11	−1.6 (5)
Cl1—C2—C3—C4	−178.1 (3)	C8—C9—C10—C11	179.1 (3)
C2—C3—C4—C5	−0.2 (6)	C9—C10—C11—C12	1.4 (6)
C3—C4—C5—C6	0.3 (6)	C10—C11—C12—C13	−0.1 (6)
C4—C5—C6—C1	−0.7 (6)	C10—C11—C12—Br1	−179.0 (3)
C2—C1—C6—C5	1.0 (5)	C11—C12—C13—C14	−1.0 (5)
C7—C1—C6—C5	−179.9 (3)	Br1—C12—C13—C14	177.9 (2)
N2—N1—C7—C1	179.2 (2)	C12—C13—C14—C9	0.8 (5)
C2—C1—C7—N1	160.0 (3)	C10—C9—C14—C13	0.5 (5)
C6—C1—C7—N1	−19.1 (4)	C8—C9—C14—C13	179.7 (3)
N1—N2—C8—O1	1.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.12	2.918 (3)	154

Symmetry code: (i) x, −y+3/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₄H₁₀BrClN₂O
M_r	337.60
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.218 (4), 13.512 (5), 9.200 (3)
β (°)	97.077 (6)
V (Å³)	1383.9 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.16
Crystal size (mm)	0.23 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Siemens, 1996)
T_min, T_max	0.491, 0.531
No. of measured, independent and observed [I > 2σ(I)] reflections	6907, 2438, 1948
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.035, 0.094, 1.03
No. of reflections	2438
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.39

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1ⁱ	0.86	2.12	2.918 (3)	154

Symmetry code: (i) x, −y+3/2, z+1/2.

Acknowledgements

This work is supported in part by a grant from the Department of Education of Liaoning, China (05 L122).

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bhandari, S. V., Bothara, K. G., Raut, M. K., Patil, A. A., Sarkate, A. P. & Mokale, V. J. (2008). Bioorg. Med. Chem. 16, 1822–1831. Web of Science CrossRef PubMed CAS Google Scholar
Pan, F.-Y. & Yang, J.-G. (2005). Acta Cryst. E61, o354–o355. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART, SAINT and SADABS. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Sinha, D., Tiwari, A. K., Singh, S., Shukla, G., Mishra, P., Chandra, H. & Mishra, A. K. (2008). Eur. J. Med. Chem. 43, 160–165. Web of Science CrossRef PubMed CAS Google Scholar