(E)-N′-(5-Bromo-2-meth­oxy­benzyl­idene)-2-chloro­benzohydrazide

Li, X.-Y.

doi:10.1107/S1600536811034623

organic compounds

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Volume 67| Part 9| September 2011| Page o2511

doi:10.1107/S1600536811034623

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(E)-N′-(5-Bromo-2-methoxybenzylidene)-2-chlorobenzohydrazide

Xiao-Yan Li ^a ^*

^aZibo Vocational Institute, Zibo 255314, People's Republic of China
^*Correspondence e-mail: lixiaoyan_zb@126.com

(Received 27 July 2011; accepted 23 August 2011; online 27 August 2011)

In the title compound, C₁₅H₁₂BrClN₂O₂, the dihedral angle between the two substituted aromatic rings is 77.8 (3)°. The molecule exists in a trans conformation with respect to the methylidene unit. In the crystal structure, inversion dimers linked by pairs of N—H⋯O hydrogen bonds generate R₂⁸(8) loops.

Related literature

For the crystal structures of some related hydrazone compounds, see: Li (2011a ,b ); Hashemian et al. (2011 ); Lei (2011 ); Shalash et al. (2010 ). For hydrogen-bond notation, see: Bernstein et al. (1995 ).

Experimental

Crystal data

C₁₅H₁₂BrClN₂O₂
M_r = 367.63
Monoclinic, P 2₁ /c
a = 11.312 (2) Å
b = 7.374 (2) Å
c = 17.979 (3) Å
β = 91.972 (3)°
V = 1499.0 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.93 mm⁻¹
T = 298 K
0.12 × 0.10 × 0.07 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.720, T_max = 0.821
5249 measured reflections
2451 independent reflections
1877 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.094
S = 1.04
2451 reflections
194 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.46 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O2ⁱ	0.89 (1)	1.99 (1)	2.882 (4)	175 (4)
Symmetry code: (i) -x, -y+1, -z.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); 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/S1600536811034623/hb6337sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811034623/hb6337Isup2.hkl

checkCIF report

Comment top

In the last few years, hydrazones have been attracted much attention for their crystal structures (e.g. Li, 2011a; Hashemian et al., 2011; Lei, 2011; Shalash et al., 2010). The author reports herein the crystal structure of the title new hydrazone compound, (I).

In the title compound, Fig. 1, the dihedral angle between the two substituted aromatic rings is 77.8 (3)°. The molecule exists in a trans configuration with respect to the methylidene unit. The bond values are comparable to those observed in a similar compound the author reported recently (Li, 2011b). In the crystal structure, adjacent two molecules are linked through two intermolecular N—H···O hydrogen bonds (Table 1), forming a dimer (Fig. 2).

Related literature top

For the crystal structures of some related hydrazone compounds, see: Li (2011a); Hashemian et al. (2011); Lei (2011); Shalash et al. (2010); Li (2011b). For hydrogen-bond notation, see: Bernstein et al. (1995).

Experimental top

A mixture of 2-chlorobenzhydrazide (0.171 g, 1 mmol) and 5-bromo-2-methoxybenzaldehyde (0.215 g, 1 mmol) in 30 ml of ethanol containing few drops of acetic acid was refluxed for about 1 h. On cooling to room temperature, a solid precipitate was formed. The solid was filtered and then recrystallized from methanol. Colorless blocks of (I) were obtained by slow evaporation of the solution.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); 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) at 30% probability level. Hydrogen bonds are indicated by dashed lines.
	Fig. 2. The packing of (I), viewed along the c axis. Intermolecular hydrogen bonds are drawn as dashed lines.

(E)-N'-(5-Bromo-2-methoxybenzylidene)-2-chlorobenzohydrazide top

Crystal data top

C₁₅H₁₂BrClN₂O₂	F(000) = 736
M_r = 367.63	D_x = 1.629 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 11.312 (2) Å	Cell parameters from 1972 reflections
b = 7.374 (2) Å	θ = 3.1–24.9°
c = 17.979 (3) Å	µ = 2.93 mm⁻¹
β = 91.972 (3)°	T = 298 K
V = 1499.0 (5) Å³	Block, colourless
Z = 4	0.12 × 0.10 × 0.07 mm

Data collection top

Bruker SMART CCD diffractometer	2451 independent reflections
Radiation source: fine-focus sealed tube	1877 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ω scans	θ_max = 25.0°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.720, T_max = 0.821	k = −8→6
5249 measured reflections	l = −20→18

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0429P)² + 0.678P] where P = (F_o² + 2F_c²)/3
2451 reflections	(Δ/σ)_max = 0.001
194 parameters	Δρ_max = 0.46 e Å⁻³
1 restraint	Δρ_min = −0.46 e Å⁻³

Crystal data top

C₁₅H₁₂BrClN₂O₂	V = 1499.0 (5) Å³
M_r = 367.63	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.312 (2) Å	µ = 2.93 mm⁻¹
b = 7.374 (2) Å	T = 298 K
c = 17.979 (3) Å	0.12 × 0.10 × 0.07 mm
β = 91.972 (3)°

Data collection top

Bruker SMART CCD diffractometer	2451 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1877 reflections with I > 2σ(I)
T_min = 0.720, T_max = 0.821	R_int = 0.050
5249 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	1 restraint
wR(F²) = 0.094	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.46 e Å⁻³
2451 reflections	Δρ_min = −0.46 e Å⁻³
194 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	0.68536 (3)	0.08870 (6)	0.13010 (2)	0.05792 (18)
Cl1	0.20872 (10)	0.35802 (17)	0.20909 (7)	0.0738 (4)
N1	0.2386 (2)	0.2805 (4)	0.03030 (15)	0.0362 (6)
N2	0.1252 (2)	0.3513 (4)	0.02797 (16)	0.0405 (7)
O1	0.4312 (2)	0.3783 (4)	−0.14532 (14)	0.0534 (7)
O2	−0.05797 (18)	0.3567 (3)	0.07125 (14)	0.0533 (7)
C1	0.4308 (2)	0.2898 (4)	−0.02015 (18)	0.0358 (7)
C2	0.4949 (3)	0.3117 (5)	−0.08532 (19)	0.0402 (8)
C3	0.6132 (3)	0.2662 (5)	−0.0855 (2)	0.0484 (9)
H3	0.6552	0.2811	−0.1287	0.058*
C4	0.6700 (3)	0.1984 (5)	−0.0217 (2)	0.0468 (9)
H4	0.7496	0.1668	−0.0221	0.056*
C5	0.6074 (3)	0.1783 (5)	0.04254 (19)	0.0401 (8)
C6	0.4885 (3)	0.2236 (4)	0.04331 (19)	0.0390 (8)
H6	0.4472	0.2093	0.0868	0.047*
C7	0.3058 (3)	0.3422 (4)	−0.01972 (19)	0.0375 (8)
H7	0.2752	0.4208	−0.0560	0.045*
C8	0.0425 (2)	0.2909 (4)	0.07350 (18)	0.0362 (7)
C9	0.0717 (2)	0.1349 (4)	0.12478 (18)	0.0348 (8)
C10	0.1435 (3)	0.1509 (5)	0.1879 (2)	0.0445 (9)
C11	0.1611 (3)	0.0055 (7)	0.2367 (2)	0.0578 (11)
H11	0.2078	0.0194	0.2799	0.069*
C12	0.1087 (4)	−0.1580 (6)	0.2202 (3)	0.0627 (12)
H12	0.1215	−0.2560	0.2521	0.075*
C13	0.0377 (4)	−0.1789 (6)	0.1573 (3)	0.0613 (11)
H13	0.0037	−0.2910	0.1465	0.074*
C14	0.0166 (3)	−0.0332 (5)	0.1098 (2)	0.0476 (9)
H14	−0.0338	−0.0464	0.0682	0.057*
C15	0.4912 (4)	0.4085 (6)	−0.2124 (2)	0.0649 (12)
H15A	0.5509	0.4995	−0.2042	0.097*
H15B	0.4357	0.4488	−0.2505	0.097*
H15C	0.5276	0.2977	−0.2278	0.097*
H2	0.109 (4)	0.444 (4)	−0.0024 (19)	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0437 (2)	0.0720 (3)	0.0575 (3)	0.00185 (18)	−0.00739 (17)	0.0012 (2)
Cl1	0.0748 (7)	0.0728 (8)	0.0728 (8)	−0.0254 (6)	−0.0124 (6)	−0.0101 (6)
N1	0.0305 (12)	0.0354 (16)	0.0430 (17)	0.0034 (11)	0.0047 (11)	0.0041 (13)
N2	0.0293 (13)	0.0413 (17)	0.051 (2)	0.0057 (11)	0.0055 (12)	0.0133 (14)
O1	0.0489 (14)	0.0648 (18)	0.0473 (16)	0.0000 (12)	0.0109 (12)	0.0140 (13)
O2	0.0318 (12)	0.0558 (16)	0.0728 (19)	0.0101 (11)	0.0087 (11)	0.0244 (14)
C1	0.0330 (15)	0.0330 (18)	0.042 (2)	−0.0017 (13)	0.0054 (14)	−0.0016 (15)
C2	0.0435 (18)	0.035 (2)	0.042 (2)	−0.0066 (15)	0.0062 (15)	−0.0031 (16)
C3	0.0410 (18)	0.051 (2)	0.054 (2)	−0.0043 (16)	0.0197 (17)	−0.0017 (19)
C4	0.0323 (16)	0.048 (2)	0.061 (3)	−0.0004 (15)	0.0104 (16)	−0.0026 (19)
C5	0.0356 (16)	0.0345 (19)	0.050 (2)	−0.0040 (14)	0.0011 (15)	−0.0035 (16)
C6	0.0347 (16)	0.0371 (19)	0.046 (2)	−0.0060 (14)	0.0086 (15)	−0.0037 (16)
C7	0.0392 (17)	0.0310 (18)	0.042 (2)	0.0000 (13)	0.0045 (15)	0.0010 (15)
C8	0.0312 (15)	0.0343 (19)	0.043 (2)	−0.0012 (13)	−0.0012 (13)	0.0042 (15)
C9	0.0285 (15)	0.0348 (19)	0.042 (2)	0.0046 (12)	0.0089 (14)	0.0051 (15)
C10	0.0339 (16)	0.050 (2)	0.049 (2)	0.0010 (15)	0.0013 (16)	−0.0007 (18)
C11	0.047 (2)	0.075 (3)	0.051 (3)	0.014 (2)	0.0002 (17)	0.017 (2)
C12	0.056 (2)	0.062 (3)	0.071 (3)	0.012 (2)	0.012 (2)	0.031 (2)
C13	0.067 (3)	0.039 (2)	0.079 (3)	−0.0035 (19)	0.017 (2)	0.010 (2)
C14	0.0476 (19)	0.044 (2)	0.051 (2)	−0.0011 (16)	0.0098 (17)	0.0049 (18)
C15	0.066 (2)	0.079 (3)	0.050 (3)	−0.011 (2)	0.014 (2)	0.012 (2)

Geometric parameters (Å, º) top

Br1—C5	1.897 (3)	C5—C6	1.386 (4)
Cl1—C10	1.733 (4)	C6—H6	0.9300
N1—C7	1.282 (4)	C7—H7	0.9300
N1—N2	1.384 (3)	C8—C9	1.504 (4)
N2—C8	1.340 (4)	C9—C10	1.377 (5)
N2—H2	0.893 (10)	C9—C14	1.409 (5)
O1—C2	1.368 (4)	C10—C11	1.395 (5)
O1—C15	1.422 (4)	C11—C12	1.371 (6)
O2—C8	1.235 (3)	C11—H11	0.9300
C1—C6	1.384 (5)	C12—C13	1.373 (6)
C1—C2	1.408 (4)	C12—H12	0.9300
C1—C7	1.466 (4)	C13—C14	1.388 (5)
C2—C3	1.380 (5)	C13—H13	0.9300
C3—C4	1.390 (5)	C14—H14	0.9300
C3—H3	0.9300	C15—H15A	0.9600
C4—C5	1.384 (5)	C15—H15B	0.9600
C4—H4	0.9300	C15—H15C	0.9600

C7—N1—N2	114.6 (3)	O2—C8—C9	120.2 (3)
C8—N2—N1	121.5 (3)	N2—C8—C9	119.0 (3)
C8—N2—H2	120 (3)	C10—C9—C14	118.5 (3)
N1—N2—H2	119 (3)	C10—C9—C8	123.4 (3)
C2—O1—C15	118.1 (3)	C14—C9—C8	118.0 (3)
C6—C1—C2	119.0 (3)	C9—C10—C11	121.3 (4)
C6—C1—C7	121.1 (3)	C9—C10—Cl1	119.4 (3)
C2—C1—C7	119.9 (3)	C11—C10—Cl1	119.2 (3)
O1—C2—C3	124.7 (3)	C12—C11—C10	119.3 (4)
O1—C2—C1	115.2 (3)	C12—C11—H11	120.4
C3—C2—C1	120.1 (3)	C10—C11—H11	120.4
C2—C3—C4	120.4 (3)	C11—C12—C13	120.8 (4)
C2—C3—H3	119.8	C11—C12—H12	119.6
C4—C3—H3	119.8	C13—C12—H12	119.6
C5—C4—C3	119.5 (3)	C12—C13—C14	120.2 (4)
C5—C4—H4	120.2	C12—C13—H13	119.9
C3—C4—H4	120.2	C14—C13—H13	119.9
C4—C5—C6	120.5 (3)	C13—C14—C9	119.9 (4)
C4—C5—Br1	119.5 (2)	C13—C14—H14	120.1
C6—C5—Br1	120.0 (3)	C9—C14—H14	120.1
C1—C6—C5	120.5 (3)	O1—C15—H15A	109.5
C1—C6—H6	119.8	O1—C15—H15B	109.5
C5—C6—H6	119.8	H15A—C15—H15B	109.5
N1—C7—C1	120.4 (3)	O1—C15—H15C	109.5
N1—C7—H7	119.8	H15A—C15—H15C	109.5
C1—C7—H7	119.8	H15B—C15—H15C	109.5
O2—C8—N2	120.7 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O2ⁱ	0.89 (1)	1.99 (1)	2.882 (4)	175 (4)

Symmetry code: (i) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂BrClN₂O₂
M_r	367.63
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	11.312 (2), 7.374 (2), 17.979 (3)
β (°)	91.972 (3)
V (Å³)	1499.0 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.93
Crystal size (mm)	0.12 × 0.10 × 0.07

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.720, 0.821
No. of measured, independent and observed [I > 2σ(I)] reflections	5249, 2451, 1877
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.094, 1.04
No. of reflections	2451
No. of parameters	194
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)	0.46, −0.46

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), 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···O2ⁱ	0.893 (10)	1.992 (12)	2.882 (4)	175 (4)

Symmetry code: (i) −x, −y+1, −z.

Acknowledgements

The author acknowledges the Zibo Vocational Institute for supporting this work.

References

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