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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 8| August 2009| Page o1750
doi:10.1107/S1600536809024921

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

Hongqi Li,a* B. K. Sarojini,b B. Narayana,c H. S. Yathirajand and William T. A. Harrisone

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[Narayana, B., Siddaraju, B. P., Raju, C. R., Yathirajan, H. S. & Bolte, M. (2007). Acta Cryst. E63, o3522.]); Butcher et al. (2007[Butcher, R. J., Jasinski, J. P., Narayana, B., Sunil, K. & Yathirajan, H. S. (2007). Acta Cryst. E63, o3652.]).

[Scheme 1]

Experimental

Crystal data

  • C15H12Br2N2O2

  • Mr = 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[Bruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.301, Tmax = 0.419 (expected range = 0.251–0.349)

  • 9369 measured reflections

  • 3515 independent reflections

  • 1902 reflections with I > 2σ(I)

  • Rint = 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

  • Δρmax = 0.57 e Å−3

  • Δρmin = −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[Bruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2006[Bruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); 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).

Refinement top

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.

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
[Figure 1] Fig. 1. A view of (I) with displacement ellipsoids for the non-hydrogen atoms drawn at the 50% probability level.
[Figure 2] 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
C15H12Br2N2O2F(000) = 808
Mr = 412.09Dx = 1.777 Mg m−3
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 mm−1
β = 96.114 (4)°T = 296 K
V = 1540.6 (9) Å3Block, colourless
Z = 40.30 × 0.20 × 0.20 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		3515 independent reflections
Radiation source: fine-focus sealed tube1902 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.063
ϕ 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 top
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) = 0.122 w = 1/[σ2(Fo2) + (0.0504P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.001
3515 reflectionsΔρmax = 0.57 e Å−3
195 parametersΔρmin = −0.81 e Å−3
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)
Crystal data top
C15H12Br2N2O2V = 1540.6 (9) Å3
Mr = 412.09Z = 4
Monoclinic, P21/cMo Kα radiation
a = 14.768 (5) ŵ = 5.27 mm−1
b = 12.753 (4) ÅT = 296 K
c = 8.227 (3) Å0.30 × 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)
Tmin = 0.301, Tmax = 0.419Rint = 0.063
9369 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0470 restraints
wR(F2) = 0.122H atoms treated by a mixture of independent and constrained refinement
S = 0.96Δρmax = 0.57 e Å−3
3515 reflectionsΔρmin = −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
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) top
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, º) top
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, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1i0.87 (4)2.07 (4)2.906 (4)160 (4)
Symmetry code: (i) x, −y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC15H12Br2N2O2
Mr412.09
Crystal system, space groupMonoclinic, 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)
Z4
Radiation typeMo Kα
µ (mm−1)5.27
Crystal size (mm)0.30 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2006)
Tmin, Tmax0.301, 0.419
No. of measured, independent and
observed [I > 2σ(I)] reflections		9369, 3515, 1902
Rint0.063
(sin θ/λ)max (Å−1)0.650
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.047, 0.122, 0.96
No. of reflections3515
No. of parameters195
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (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···AD—HH···AD···AD—H···A
N1—H1···O1i0.87 (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

First citationBruker (2006). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationButcher, R. J., Jasinski, J. P., Narayana, B., Sunil, K. & Yathirajan, H. S. (2007). Acta Cryst. E63, o3652.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationNarayana, B., Siddaraju, B. P., Raju, C. R., Yathirajan, H. S. & Bolte, M. (2007). Acta Cryst. E63, o3522.  Web of Science CSD CrossRef IUCr Journals Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 65| Part 8| August 2009| Page o1750
doi:10.1107/S1600536809024921
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