2-Bromo-N′-[(Z)-2-bromo­benzyl­idene]-5-methoxy­benzohydrazide

Li, H.; Sarojini, B.K.; Narayana, B.; Yathirajan, H.S.; Harrison, W.T.A.

doi:10.1107/S1600536809024921

organic compounds

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Volume 65| Part 8| August 2009| Page o1750

doi:10.1107/S1600536809024921

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2-Bromo-N′-[(Z)-2-bromobenzylidene]-5-methoxybenzohydrazide

Hongqi Li,^a ^* B. K. Sarojini,^b B. Narayana,^c H. S. Yathirajan ^d and William T. A. Harrison ^e

^aKey Laboratory of Science & Technology of Eco-Textiles, Ministry of Education, College of Chemistry, Chemical Engineering & Biotechnology, Donghua University, Shanghai 201620, People's Republic of China, ^bDepartment of Chemistry, P. A. College of Engineering, Mangalore 574 153, India, ^cDepartment of Studies in Chemistry, Mangalore University, Mangalagangotri 574 199, India, ^dDepartment of Studies in Chemistry, University of Mysore, Manasagangotri, Mysore 570 006, India, and ^eDepartment of Chemistry, University of Aberdeen, Aberdeen AB24 3UE, Scotland
^*Correspondence e-mail: hongqili@dhu.edu.cn

(Received 26 June 2009; accepted 29 June 2009; online 4 July 2009)

In the title compound, C₁₅H₁₂Br₂N₂O₂, the molecule adopts an E conformation about the C=N double bond and a transoid conformation about the central N—N bond, with a C(=O)—N—N—C(H) dihedral angle of 169.4 (4)°. In the crystal, molecules are linked by N—H⋯O hydrogen bonds, leading to C(4) chains. The packing also features slipped π–π stacking interactions, with a centroid–centroid separation of 3.838 (3) Å and a slippage of 1.19 Å.

Related literature

For related structures and background, see: Narayana et al. (2007 ); Butcher et al. (2007 ).

Experimental

Crystal data

C₁₅H₁₂Br₂N₂O₂
M_r = 412.09
Monoclinic, P 2₁ /c
a = 14.768 (5) Å
b = 12.753 (4) Å
c = 8.227 (3) Å
β = 96.114 (4)°
V = 1540.6 (9) Å³
Z = 4
Mo Kα radiation
μ = 5.27 mm⁻¹
T = 296 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ) T_min = 0.301, T_max = 0.419 (expected range = 0.251–0.349)
9369 measured reflections
3515 independent reflections
1902 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.122
S = 0.96
3515 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.57 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.87 (4)	2.07 (4)	2.906 (4)	160 (4)
Symmetry code: (i) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); 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/S1600536809024921/fj2231sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809024921/fj2231Isup2.hkl

checkCIF report

Comment top

As part of our ongoing studies of substituted benzohydrazides (Narayana et al., 2007; Butcher et al., 2007) we now describe the synthesis and crystal structure of the title compound, (I) (Fig. 1).

The dihedral angle between the mean planes of the A (C1–C6) and B (C10–C15) rings is 18.6 (3)°. Atom C7 is dispalaced from the A plane by 0.064 (9)Å. The molecule is significantly twisted about the N1—N2 bond.

In the crystal, an intermolecular N—H···O interaction occurs (Table 2), leading to C(4) chains (Fig. 2) of molecules propagating in [001]. The shortest intermolecular aromatic ring centroid–centroid separation is 3.638 (3)Å, indicative of weak π-π stacking.

Related literature top

For related structures and background, see: Narayana et al. (2007); Butcher et al. (2007).

Experimental top

A mixture of 2-bromobenzaldehyde (1.85 g, 0.01 mol) and 2-bromo-5-methoxybenzo-hydrazide (2.45 g, 0.01mol) in 15 ml of ethanol containing 2 drops of 4 M hydrochloric acid was refluxed for 3 hours. On cooling, the solid separated was filtered and recrystallized from ethyl alcohol to yield colourless blocks of (I) (m.p: 440-442 K). Analysis (%) for C₁₅H₁₂Br₂N₂O₂: calculated (found): C 43.73 (43.66), H 2.94 (2.91), N 6.80 (6.76).

Computing details top

Data collection: SMART (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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. A view of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
	Fig. 2. A fragment of an [001] C(4) chain of molcules in the crystal of (I). Symmetry code as in Table 2.

2-Bromo-N'-[(Z)-2-bromobenzylidene]-5-methoxybenzohydrazide top

Crystal data top

C₁₅H₁₂Br₂N₂O₂	F(000) = 808
M_r = 412.09	D_x = 1.777 Mg m⁻³
Monoclinic, P2₁/c	Melting point = 440–442 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.768 (5) Å	Cell parameters from 1776 reflections
b = 12.753 (4) Å	θ = 2.8–22.8°
c = 8.227 (3) Å	µ = 5.27 mm⁻¹
β = 96.114 (4)°	T = 296 K
V = 1540.6 (9) Å³	Block, colourless
Z = 4	0.30 × 0.20 × 0.20 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3515 independent reflections
Radiation source: fine-focus sealed tube	1902 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 27.5°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −19→14
T_min = 0.301, T_max = 0.419	k = −12→16
9369 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.122	w = 1/[σ²(F_o²) + (0.0504P)²] where P = (F_o² + 2F_c²)/3
S = 0.96	(Δ/σ)_max = 0.001
3515 reflections	Δρ_max = 0.57 e Å⁻³
195 parameters	Δρ_min = −0.81 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0145 (10)

Crystal data top

C₁₅H₁₂Br₂N₂O₂	V = 1540.6 (9) Å³
M_r = 412.09	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.768 (5) Å	µ = 5.27 mm⁻¹
b = 12.753 (4) Å	T = 296 K
c = 8.227 (3) Å	0.30 × 0.20 × 0.20 mm
β = 96.114 (4)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3515 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2006)	1902 reflections with I > 2σ(I)
T_min = 0.301, T_max = 0.419	R_int = 0.063
9369 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.122	H atoms treated by a mixture of independent and constrained refinement
S = 0.96	Δρ_max = 0.57 e Å⁻³
3515 reflections	Δρ_min = −0.81 e Å⁻³
195 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
C1	0.1558 (3)	0.0150 (3)	0.5766 (5)	0.0405 (11)
C2	0.1498 (3)	0.1213 (3)	0.5376 (5)	0.0322 (9)
C3	0.0842 (3)	0.1808 (3)	0.6039 (5)	0.0367 (10)
H3	0.0794	0.2520	0.5796	0.044*
C4	0.0256 (3)	0.1365 (3)	0.7055 (5)	0.0415 (11)
C5	0.0317 (3)	0.0314 (4)	0.7407 (6)	0.0536 (13)
H5	−0.0084	0.0006	0.8065	0.064*
C6	0.0973 (3)	−0.0282 (4)	0.6780 (6)	0.0522 (12)
H6	0.1024	−0.0990	0.7045	0.063*
C7	−0.0958 (3)	0.1633 (4)	0.8725 (6)	0.0655 (15)
H7A	−0.1332	0.1093	0.8189	0.098*
H7B	−0.1339	0.2188	0.9054	0.098*
H7C	−0.0608	0.1347	0.9672	0.098*
C8	0.2084 (3)	0.1719 (3)	0.4227 (5)	0.0356 (10)
C9	0.3247 (3)	0.4087 (4)	0.4401 (5)	0.0406 (10)
H9	0.2985	0.4355	0.5293	0.049*
C10	0.3904 (3)	0.4723 (3)	0.3608 (5)	0.0374 (10)
C11	0.3967 (3)	0.5806 (4)	0.3780 (6)	0.0477 (11)
C12	0.4617 (4)	0.6382 (4)	0.3079 (7)	0.0646 (15)
H12	0.4641	0.7107	0.3198	0.077*
C13	0.5223 (4)	0.5874 (5)	0.2207 (7)	0.0712 (17)
H13	0.5668	0.6254	0.1742	0.085*
C14	0.5179 (4)	0.4814 (5)	0.2017 (7)	0.0708 (16)
H14	0.5590	0.4475	0.1415	0.085*
C15	0.4530 (3)	0.4241 (4)	0.2707 (6)	0.0527 (13)
H15	0.4510	0.3517	0.2568	0.063*
Br1	0.24530 (3)	−0.07259 (4)	0.49919 (6)	0.0578 (2)
Br2	0.31365 (4)	0.65524 (4)	0.49486 (9)	0.0861 (3)
O1	0.2174 (2)	0.1358 (2)	0.2869 (3)	0.0489 (8)
O2	−0.0358 (2)	0.2037 (3)	0.7627 (4)	0.0579 (9)
N1	0.2468 (2)	0.2623 (3)	0.4809 (4)	0.0400 (9)
H1	0.239 (3)	0.277 (3)	0.582 (5)	0.048*
N2	0.3036 (2)	0.3173 (3)	0.3872 (4)	0.0391 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.038 (3)	0.042 (3)	0.042 (3)	−0.002 (2)	0.011 (2)	−0.007 (2)
C2	0.030 (2)	0.037 (2)	0.030 (2)	−0.0044 (18)	0.0070 (18)	−0.0026 (18)
C3	0.038 (2)	0.036 (2)	0.038 (2)	0.0012 (19)	0.0104 (19)	0.0061 (19)
C4	0.036 (2)	0.046 (3)	0.044 (3)	0.000 (2)	0.012 (2)	0.003 (2)
C5	0.056 (3)	0.051 (3)	0.060 (3)	−0.010 (2)	0.034 (3)	0.004 (3)
C6	0.056 (3)	0.038 (3)	0.066 (3)	−0.005 (2)	0.020 (3)	0.008 (2)
C7	0.051 (3)	0.080 (4)	0.071 (4)	−0.002 (3)	0.035 (3)	0.000 (3)
C8	0.035 (2)	0.037 (3)	0.035 (2)	−0.0032 (19)	0.0082 (19)	0.007 (2)
C9	0.037 (2)	0.044 (3)	0.043 (3)	0.003 (2)	0.017 (2)	−0.001 (2)
C10	0.033 (2)	0.039 (3)	0.042 (2)	0.0010 (19)	0.0143 (19)	0.006 (2)
C11	0.037 (2)	0.043 (3)	0.064 (3)	−0.002 (2)	0.011 (2)	0.006 (2)
C12	0.057 (3)	0.056 (3)	0.080 (4)	−0.014 (3)	0.006 (3)	0.019 (3)
C13	0.055 (3)	0.091 (5)	0.070 (4)	−0.022 (3)	0.020 (3)	0.026 (3)
C14	0.051 (3)	0.100 (5)	0.068 (4)	0.001 (3)	0.035 (3)	0.012 (3)
C15	0.048 (3)	0.056 (3)	0.058 (3)	0.005 (2)	0.027 (2)	0.004 (2)
Br1	0.0569 (4)	0.0486 (3)	0.0713 (4)	0.0116 (2)	0.0227 (3)	−0.0006 (2)
Br2	0.0675 (4)	0.0502 (4)	0.1467 (7)	0.0080 (3)	0.0393 (4)	−0.0194 (4)
O1	0.066 (2)	0.050 (2)	0.0337 (17)	−0.0067 (16)	0.0203 (15)	−0.0084 (15)
O2	0.0502 (19)	0.059 (2)	0.071 (2)	0.0080 (17)	0.0370 (17)	0.0058 (18)
N1	0.044 (2)	0.045 (2)	0.035 (2)	−0.0083 (17)	0.0204 (18)	−0.0031 (18)
N2	0.039 (2)	0.044 (2)	0.038 (2)	−0.0050 (17)	0.0188 (16)	0.0016 (17)

Geometric parameters (Å, º) top

C1—C6	1.378 (6)	C8—N1	1.350 (5)
C1—C2	1.394 (6)	C9—N2	1.272 (5)
C1—Br1	1.892 (4)	C9—C10	1.469 (6)
C2—C3	1.387 (5)	C9—H9	0.9300
C2—C8	1.495 (5)	C10—C15	1.388 (6)
C3—C4	1.386 (5)	C10—C11	1.390 (6)
C3—H3	0.9300	C11—C12	1.382 (6)
C4—O2	1.367 (5)	C11—Br2	1.894 (5)
C4—C5	1.373 (6)	C12—C13	1.369 (8)
C5—C6	1.375 (6)	C12—H12	0.9300
C5—H5	0.9300	C13—C14	1.361 (8)
C6—H6	0.9300	C13—H13	0.9300
C7—O2	1.427 (5)	C14—C15	1.375 (7)
C7—H7A	0.9600	C14—H14	0.9300
C7—H7B	0.9600	C15—H15	0.9300
C7—H7C	0.9600	N1—N2	1.388 (4)
C8—O1	1.229 (5)	N1—H1	0.87 (4)

C6—C1—C2	120.0 (4)	N2—C9—C10	120.3 (4)
C6—C1—Br1	118.2 (3)	N2—C9—H9	119.9
C2—C1—Br1	121.8 (3)	C10—C9—H9	119.9
C3—C2—C1	118.2 (3)	C15—C10—C11	116.9 (4)
C3—C2—C8	119.2 (4)	C15—C10—C9	120.1 (4)
C1—C2—C8	122.6 (3)	C11—C10—C9	122.9 (4)
C4—C3—C2	121.4 (4)	C12—C11—C10	121.9 (4)
C4—C3—H3	119.3	C12—C11—Br2	117.4 (4)
C2—C3—H3	119.3	C10—C11—Br2	120.7 (3)
O2—C4—C5	124.8 (4)	C13—C12—C11	119.2 (5)
O2—C4—C3	115.6 (4)	C13—C12—H12	120.4
C5—C4—C3	119.6 (4)	C11—C12—H12	120.4
C4—C5—C6	119.6 (4)	C14—C13—C12	120.3 (5)
C4—C5—H5	120.2	C14—C13—H13	119.9
C6—C5—H5	120.2	C12—C13—H13	119.9
C5—C6—C1	121.2 (4)	C13—C14—C15	120.5 (5)
C5—C6—H6	119.4	C13—C14—H14	119.7
C1—C6—H6	119.4	C15—C14—H14	119.7
O2—C7—H7A	109.5	C14—C15—C10	121.2 (5)
O2—C7—H7B	109.5	C14—C15—H15	119.4
H7A—C7—H7B	109.5	C10—C15—H15	119.4
O2—C7—H7C	109.5	C4—O2—C7	118.1 (4)
H7A—C7—H7C	109.5	C8—N1—N2	119.4 (3)
H7B—C7—H7C	109.5	C8—N1—H1	115 (3)
O1—C8—N1	124.1 (4)	N2—N1—H1	125 (3)
O1—C8—C2	122.7 (4)	C9—N2—N1	114.5 (3)
N1—C8—C2	113.2 (4)

C6—C1—C2—C3	0.2 (6)	N2—C9—C10—C11	160.4 (4)
Br1—C1—C2—C3	−177.8 (3)	C15—C10—C11—C12	0.5 (7)
C6—C1—C2—C8	−177.3 (4)	C9—C10—C11—C12	177.2 (4)
Br1—C1—C2—C8	4.7 (6)	C15—C10—C11—Br2	178.8 (3)
C1—C2—C3—C4	−0.3 (6)	C9—C10—C11—Br2	−4.4 (6)
C8—C2—C3—C4	177.2 (4)	C10—C11—C12—C13	−0.8 (8)
C2—C3—C4—O2	180.0 (4)	Br2—C11—C12—C13	−179.2 (4)
C2—C3—C4—C5	−0.6 (7)	C11—C12—C13—C14	0.8 (8)
O2—C4—C5—C6	−179.0 (4)	C12—C13—C14—C15	−0.5 (9)
C3—C4—C5—C6	1.7 (7)	C13—C14—C15—C10	0.2 (8)
C4—C5—C6—C1	−1.8 (8)	C11—C10—C15—C14	−0.2 (7)
C2—C1—C6—C5	0.9 (7)	C9—C10—C15—C14	−177.0 (5)
Br1—C1—C6—C5	179.0 (4)	C5—C4—O2—C7	2.8 (7)
C3—C2—C8—O1	−127.5 (4)	C3—C4—O2—C7	−177.8 (4)
C1—C2—C8—O1	50.0 (6)	O1—C8—N1—N2	−2.9 (6)
C3—C2—C8—N1	50.2 (5)	C2—C8—N1—N2	179.5 (3)
C1—C2—C8—N1	−132.4 (4)	C10—C9—N2—N1	174.9 (4)
N2—C9—C10—C15	−23.0 (7)	C8—N1—N2—C9	169.4 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.87 (4)	2.07 (4)	2.906 (4)	160 (4)

Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂Br₂N₂O₂
M_r	412.09
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	14.768 (5), 12.753 (4), 8.227 (3)
β (°)	96.114 (4)
V (Å³)	1540.6 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	5.27
Crystal size (mm)	0.30 × 0.20 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2006)
T_min, T_max	0.301, 0.419
No. of measured, independent and observed [I > 2σ(I)] reflections	9369, 3515, 1902
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.122, 0.96
No. of reflections	3515
No. of parameters	195
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.57, −0.81

Computer programs: SMART (Bruker, 2006), SAINT (Bruker, 2006), 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
N1—H1···O1ⁱ	0.87 (4)	2.07 (4)	2.906 (4)	160 (4)

Symmetry code: (i) x, −y+1/2, z+1/2.

Acknowledgements

HSY thanks the University of Mysore for research facilities.

References

Bruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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