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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): o1750.
Published online 2009 July 4. doi:  10.1107/S1600536809024921
PMCID: PMC2977412

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 [triangle]); Butcher et al. (2007 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-o1750-scheme1.jpg

Experimental

Crystal data

  • C15H12Br2N2O2
  • M r = 412.09
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-o1750-efi1.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.57 e Å−3
  • Δρmin = −0.81 e Å−3

Data collection: SMART (Bruker, 2006 [triangle]); cell refinement: SAINT (Bruker, 2006 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809024921/fj2231sup1.cif

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

HSY thanks the University of Mysore for research facilities.

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 Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(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

C15H12Br2N2O2F(000) = 808
Mr = 412.09Dx = 1.777 Mg m3
Monoclinic, P21/cMelting point = 440–442 K
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 14.768 (5) ÅCell parameters from 1776 reflections
b = 12.753 (4) Åθ = 2.8–22.8°
c = 8.227 (3) ŵ = 5.27 mm1
β = 96.114 (4)°T = 296 K
V = 1540.6 (9) Å3Block, colourless
Z = 40.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer3515 independent reflections
Radiation source: fine-focus sealed tube1902 reflections with I > 2σ(I)
graphiteRint = 0.063
[var phi] and ω scansθmax = 27.5°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2006)h = −19→14
Tmin = 0.301, Tmax = 0.419k = −12→16
9369 measured reflectionsl = −10→10

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.122w = 1/[σ2(Fo2) + (0.0504P)2] where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
3515 reflectionsΔρmax = 0.57 e Å3
195 parametersΔρmin = −0.81 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction 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 (Å2)

xyzUiso*/Ueq
C10.1558 (3)0.0150 (3)0.5766 (5)0.0405 (11)
C20.1498 (3)0.1213 (3)0.5376 (5)0.0322 (9)
C30.0842 (3)0.1808 (3)0.6039 (5)0.0367 (10)
H30.07940.25200.57960.044*
C40.0256 (3)0.1365 (3)0.7055 (5)0.0415 (11)
C50.0317 (3)0.0314 (4)0.7407 (6)0.0536 (13)
H5−0.00840.00060.80650.064*
C60.0973 (3)−0.0282 (4)0.6780 (6)0.0522 (12)
H60.1024−0.09900.70450.063*
C7−0.0958 (3)0.1633 (4)0.8725 (6)0.0655 (15)
H7A−0.13320.10930.81890.098*
H7B−0.13390.21880.90540.098*
H7C−0.06080.13470.96720.098*
C80.2084 (3)0.1719 (3)0.4227 (5)0.0356 (10)
C90.3247 (3)0.4087 (4)0.4401 (5)0.0406 (10)
H90.29850.43550.52930.049*
C100.3904 (3)0.4723 (3)0.3608 (5)0.0374 (10)
C110.3967 (3)0.5806 (4)0.3780 (6)0.0477 (11)
C120.4617 (4)0.6382 (4)0.3079 (7)0.0646 (15)
H120.46410.71070.31980.077*
C130.5223 (4)0.5874 (5)0.2207 (7)0.0712 (17)
H130.56680.62540.17420.085*
C140.5179 (4)0.4814 (5)0.2017 (7)0.0708 (16)
H140.55900.44750.14150.085*
C150.4530 (3)0.4241 (4)0.2707 (6)0.0527 (13)
H150.45100.35170.25680.063*
Br10.24530 (3)−0.07259 (4)0.49919 (6)0.0578 (2)
Br20.31365 (4)0.65524 (4)0.49486 (9)0.0861 (3)
O10.2174 (2)0.1358 (2)0.2869 (3)0.0489 (8)
O2−0.0358 (2)0.2037 (3)0.7627 (4)0.0579 (9)
N10.2468 (2)0.2623 (3)0.4809 (4)0.0400 (9)
H10.239 (3)0.277 (3)0.582 (5)0.048*
N20.3036 (2)0.3173 (3)0.3872 (4)0.0391 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
C10.038 (3)0.042 (3)0.042 (3)−0.002 (2)0.011 (2)−0.007 (2)
C20.030 (2)0.037 (2)0.030 (2)−0.0044 (18)0.0070 (18)−0.0026 (18)
C30.038 (2)0.036 (2)0.038 (2)0.0012 (19)0.0104 (19)0.0061 (19)
C40.036 (2)0.046 (3)0.044 (3)0.000 (2)0.012 (2)0.003 (2)
C50.056 (3)0.051 (3)0.060 (3)−0.010 (2)0.034 (3)0.004 (3)
C60.056 (3)0.038 (3)0.066 (3)−0.005 (2)0.020 (3)0.008 (2)
C70.051 (3)0.080 (4)0.071 (4)−0.002 (3)0.035 (3)0.000 (3)
C80.035 (2)0.037 (3)0.035 (2)−0.0032 (19)0.0082 (19)0.007 (2)
C90.037 (2)0.044 (3)0.043 (3)0.003 (2)0.017 (2)−0.001 (2)
C100.033 (2)0.039 (3)0.042 (2)0.0010 (19)0.0143 (19)0.006 (2)
C110.037 (2)0.043 (3)0.064 (3)−0.002 (2)0.011 (2)0.006 (2)
C120.057 (3)0.056 (3)0.080 (4)−0.014 (3)0.006 (3)0.019 (3)
C130.055 (3)0.091 (5)0.070 (4)−0.022 (3)0.020 (3)0.026 (3)
C140.051 (3)0.100 (5)0.068 (4)0.001 (3)0.035 (3)0.012 (3)
C150.048 (3)0.056 (3)0.058 (3)0.005 (2)0.027 (2)0.004 (2)
Br10.0569 (4)0.0486 (3)0.0713 (4)0.0116 (2)0.0227 (3)−0.0006 (2)
Br20.0675 (4)0.0502 (4)0.1467 (7)0.0080 (3)0.0393 (4)−0.0194 (4)
O10.066 (2)0.050 (2)0.0337 (17)−0.0067 (16)0.0203 (15)−0.0084 (15)
O20.0502 (19)0.059 (2)0.071 (2)0.0080 (17)0.0370 (17)0.0058 (18)
N10.044 (2)0.045 (2)0.035 (2)−0.0083 (17)0.0204 (18)−0.0031 (18)
N20.039 (2)0.044 (2)0.038 (2)−0.0050 (17)0.0188 (16)0.0016 (17)

Geometric parameters (Å, °)

C1—C61.378 (6)C8—N11.350 (5)
C1—C21.394 (6)C9—N21.272 (5)
C1—Br11.892 (4)C9—C101.469 (6)
C2—C31.387 (5)C9—H90.9300
C2—C81.495 (5)C10—C151.388 (6)
C3—C41.386 (5)C10—C111.390 (6)
C3—H30.9300C11—C121.382 (6)
C4—O21.367 (5)C11—Br21.894 (5)
C4—C51.373 (6)C12—C131.369 (8)
C5—C61.375 (6)C12—H120.9300
C5—H50.9300C13—C141.361 (8)
C6—H60.9300C13—H130.9300
C7—O21.427 (5)C14—C151.375 (7)
C7—H7A0.9600C14—H140.9300
C7—H7B0.9600C15—H150.9300
C7—H7C0.9600N1—N21.388 (4)
C8—O11.229 (5)N1—H10.87 (4)
C6—C1—C2120.0 (4)N2—C9—C10120.3 (4)
C6—C1—Br1118.2 (3)N2—C9—H9119.9
C2—C1—Br1121.8 (3)C10—C9—H9119.9
C3—C2—C1118.2 (3)C15—C10—C11116.9 (4)
C3—C2—C8119.2 (4)C15—C10—C9120.1 (4)
C1—C2—C8122.6 (3)C11—C10—C9122.9 (4)
C4—C3—C2121.4 (4)C12—C11—C10121.9 (4)
C4—C3—H3119.3C12—C11—Br2117.4 (4)
C2—C3—H3119.3C10—C11—Br2120.7 (3)
O2—C4—C5124.8 (4)C13—C12—C11119.2 (5)
O2—C4—C3115.6 (4)C13—C12—H12120.4
C5—C4—C3119.6 (4)C11—C12—H12120.4
C4—C5—C6119.6 (4)C14—C13—C12120.3 (5)
C4—C5—H5120.2C14—C13—H13119.9
C6—C5—H5120.2C12—C13—H13119.9
C5—C6—C1121.2 (4)C13—C14—C15120.5 (5)
C5—C6—H6119.4C13—C14—H14119.7
C1—C6—H6119.4C15—C14—H14119.7
O2—C7—H7A109.5C14—C15—C10121.2 (5)
O2—C7—H7B109.5C14—C15—H15119.4
H7A—C7—H7B109.5C10—C15—H15119.4
O2—C7—H7C109.5C4—O2—C7118.1 (4)
H7A—C7—H7C109.5C8—N1—N2119.4 (3)
H7B—C7—H7C109.5C8—N1—H1115 (3)
O1—C8—N1124.1 (4)N2—N1—H1125 (3)
O1—C8—C2122.7 (4)C9—N2—N1114.5 (3)
N1—C8—C2113.2 (4)
C6—C1—C2—C30.2 (6)N2—C9—C10—C11160.4 (4)
Br1—C1—C2—C3−177.8 (3)C15—C10—C11—C120.5 (7)
C6—C1—C2—C8−177.3 (4)C9—C10—C11—C12177.2 (4)
Br1—C1—C2—C84.7 (6)C15—C10—C11—Br2178.8 (3)
C1—C2—C3—C4−0.3 (6)C9—C10—C11—Br2−4.4 (6)
C8—C2—C3—C4177.2 (4)C10—C11—C12—C13−0.8 (8)
C2—C3—C4—O2180.0 (4)Br2—C11—C12—C13−179.2 (4)
C2—C3—C4—C5−0.6 (7)C11—C12—C13—C140.8 (8)
O2—C4—C5—C6−179.0 (4)C12—C13—C14—C15−0.5 (9)
C3—C4—C5—C61.7 (7)C13—C14—C15—C100.2 (8)
C4—C5—C6—C1−1.8 (8)C11—C10—C15—C14−0.2 (7)
C2—C1—C6—C50.9 (7)C9—C10—C15—C14−177.0 (5)
Br1—C1—C6—C5179.0 (4)C5—C4—O2—C72.8 (7)
C3—C2—C8—O1−127.5 (4)C3—C4—O2—C7−177.8 (4)
C1—C2—C8—O150.0 (6)O1—C8—N1—N2−2.9 (6)
C3—C2—C8—N150.2 (5)C2—C8—N1—N2179.5 (3)
C1—C2—C8—N1−132.4 (4)C10—C9—N2—N1174.9 (4)
N2—C9—C10—C15−23.0 (7)C8—N1—N2—C9169.4 (4)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.87 (4)2.07 (4)2.906 (4)160 (4)

Symmetry codes: (i) x, −y+1/2, z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FJ2231).

References

  • Bruker (2006). SMART, SAINT and SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Butcher, R. J., Jasinski, J. P., Narayana, B., Sunil, K. & Yathirajan, H. S. (2007). Acta Cryst. E63, o3652.
  • Narayana, B., Siddaraju, B. P., Raju, C. R., Yathirajan, H. S. & Bolte, M. (2007). Acta Cryst. E63, o3522.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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