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

Abstract

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,

• a = 14.768 (5) Å

• b = 12.753 (4) Å

• c = 8.227 (3) Å

• β = 96.114 (4)°

• V = 1540.6 (9) ų

• 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[F ² > 2σ(F ²)] = 0.047

• wR(F ²) = 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

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.

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
N1—H1⋯O1i	0.87 (4)	2.07 (4)	2.906 (4)	160 (4)

Symmetry code: (i) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

The N-bound H atom was located in a difference map and its position was freely refined. All the other H atoms were placed in idealized locations (C—H = 0.93–0.98 Å) and refined as riding with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(methyl C). The methyl group was allowed to rotate, but not to tip, to best fit the electron density.

Figures

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.

Crystal data

C15H12Br2N2O2	F(000) = 808
Mr = 412.09	Dx = 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

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

Refinement

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(Fo2) + (0.0504P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96	(Δ/σ)max = 0.001
3515 reflections	Δρmax = 0.57 e Å−3
195 parameters	Δρmin = −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)

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
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 (Ų)

	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, °)

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, °)

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 codes: (i) x, −y+1/2, z+1/2.