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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o2170.
Published online 2010 July 31. doi:  10.1107/S1600536810029867
PMCID: PMC3007455

(E,E)-1,2-Bis[1-(2-bromo­phen­yl)ethyl­idene]hydrazine

Abstract

In the title compound, C16H14Br2N2, the complete molecule is generated by a crystallographic twofold axis. The dihedral angle between the two benzene rings is 35.28 (8)° and that between the best planes of two ethyl­idinehydrazine N—N=C—Me units is 87.67 (11)°. Each of these N/N/C/C planes makes a dihedral angle of 63.81 (10)° with the adjacent benzene ring. In the crystal, the mol­ecules are arranged into a layer parallel to the ac plane through C—H(...)π inter­actions. C(...)Br short contacts [3.4032 (18)–3.5969 (19) Å] are also observed.

Related literature

For bond-length data, see: Allen et al. (1987 [triangle]). For a related structure, see: Zhao et al. (2006 [triangle]). For background to and the biological activity of hydro­zones, see: Avaji et al. (2009 [triangle]); El-Tabl et al. (2008 [triangle]); Rollas & Küçükgüzel (2007 [triangle]). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 [triangle]).

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Object name is e-66-o2170-scheme1.jpg

Experimental

Crystal data

  • C16H14Br2N2
  • M r = 394.11
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2170-efi2.jpg
  • a = 17.2162 (3) Å
  • b = 11.8414 (3) Å
  • c = 7.6953 (2) Å
  • V = 1568.79 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 5.16 mm−1
  • T = 100 K
  • 0.41 × 0.27 × 0.18 mm

Data collection

  • Bruker APEXII CCD area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.227, T max = 0.462
  • 18529 measured reflections
  • 3458 independent reflections
  • 2397 reflections with I > 2σ(I)
  • R int = 0.042

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.081
  • S = 1.02
  • 3458 reflections
  • 92 parameters
  • H-atom parameters constrained
  • Δρmax = 0.75 e Å−3
  • Δρmin = −0.40 e Å−3

Data collection: APEX2 (Bruker, 2005 [triangle]); cell refinement: SAINT (Bruker, 2005 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810029867/is2578sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029867/is2578Isup2.hkl

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

Acknowledgments

PJ thanks the Center of Excellence for Innovation in Chemistry (PERCH-CIC), the Commission on Higher Education, the Ministry of Education and the Graduate School, Prince of Songkla University, for financial support. The authors thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Hydrazones are a special group of compounds in the Schiff base family and characterized by the presence of >C═N—N═C< (Avaji et al., 2009). They have been studied for their chemical and biological activities for a long time. They and their complexes show various biological activities such as insecticidal, antitumor, antioxidant, antifungal, antibacterial and antiviral properties (El-Tabl et al., 2008; Rollas & Küçükgüzel, 2007). These interesting properties prompt us to synthesise the title hydrazone derivative (I) in order to study its antibacterial activity. Herein the crystal structure of (I) was reported.

The asymmetric unit of (I) (Fig. 1), C16H14Br2N2, contains one half-molecule and the complete molecule is generated by a crystallographic symmetry centre 1 - x, y, 1/2 - z. The molecule of (I) exists in an E configuration with respect to the C7═N1 double bond [1.2812 (19) Å] and the torsion angle N1A–N1–C7–C6 = -173.12 (13)°. The dihedral angle between the two benzene rings is 35.28 (8)°. Atoms C7/C8/N1/N1A lie on a same plane [r.m.s 0.0116 (2) Å] and the torsion angle N1A–N1–C7–C8 = 3.8 (2)°. The dihedral angle between this plane and its symmetry related plane (C7A/C8A/N1/N1A) is 87.67 (11)°. Each of these two middle C/C/N/N planes makes a dihedral angle of 63.81 (10)° with its adjacent benzene ring. The bond distances are of normal values (Allen et al., 1987) and are comparable with a related structure (Zhao et al., 2006).

In the crystal structure (Fig. 2), the molecules are arranged into zigzag chains along the a axis and these chains stacked along the c direction. The molecules are consolidated by C···Br [3.4032 (18)–3.5969 (19) Å] short contacts. C—H···π interactions were also observed (Table 1); Cg1 is the centroid of C1–C6 ring.

Experimental

The title compound was synthesized by mixing a solution (1:2 molar ratio) of hydrazine hydrate (0.10 ml, 2 mmol) and 2-bromoacetophenone (0.54 ml, 4 mmol) in ethanol (20 ml). The resulting solution was refluxed for 5 h, yielding the white crystalline solid. The resultant solid was filtered off and washed with methanol. Colorless hexagonal-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from acetone by slow evaporation of the solvent at room temperature over several days (m.p. 387–389 K).

Refinement

H atoms were positioned geometrically and allowed to ride on their parent atoms, with d(C—H) = 0.93 Å for aromatic and 0.96 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl H atoms and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.

Figures

Fig. 1.
The molecular structure of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme. Atoms with suffix A were generated by symmetry code 1 - x, y, 1/2 - z.
Fig. 2.
The crystal packing of the title compound viewed along the b axis, showing zigzag chains running along the a-axis.

Crystal data

C16H14Br2N2Dx = 1.669 Mg m3
Mr = 394.11Melting point = 387–389 K
Orthorhombic, PccaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2a 2acCell parameters from 3458 reflections
a = 17.2162 (3) Åθ = 3.4–35.0°
b = 11.8414 (3) ŵ = 5.16 mm1
c = 7.6953 (2) ÅT = 100 K
V = 1568.79 (6) Å3Block, colorless
Z = 40.41 × 0.27 × 0.18 mm
F(000) = 776

Data collection

Bruker APEXII CCD area-detector diffractometer3458 independent reflections
Radiation source: sealed tube2397 reflections with I > 2σ(I)
graphiteRint = 0.042
[var phi] and ω scansθmax = 35.0°, θmin = 3.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)h = −27→27
Tmin = 0.227, Tmax = 0.462k = −19→17
18529 measured reflectionsl = −12→12

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.033P)2 + 0.5992P] where P = (Fo2 + 2Fc2)/3
3458 reflections(Δ/σ)max = 0.001
92 parametersΔρmax = 0.75 e Å3
0 restraintsΔρmin = −0.40 e Å3

Special details

Experimental. The crystal was placed in the cold stream of an Oxford Cryosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 120.0 (1) K.
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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
Br10.634618 (11)0.935005 (14)0.01020 (2)0.03110 (7)
N10.53208 (8)0.65309 (11)0.19436 (17)0.0228 (3)
C10.64389 (9)0.79361 (14)−0.1054 (2)0.0234 (3)
C20.70442 (10)0.77985 (16)−0.2228 (2)0.0294 (3)
H2A0.73830.8391−0.24590.035*
C30.71362 (10)0.67629 (16)−0.3054 (2)0.0328 (4)
H3A0.75380.6662−0.38470.039*
C40.66330 (11)0.58836 (16)−0.2698 (2)0.0312 (4)
H4A0.66950.5193−0.32560.037*
C50.60342 (10)0.60310 (15)−0.1509 (2)0.0253 (3)
H5A0.57000.5433−0.12740.030*
C60.59263 (9)0.70617 (13)−0.06618 (19)0.0209 (3)
C70.52783 (9)0.71762 (13)0.06106 (19)0.0205 (3)
C80.46160 (10)0.79632 (16)0.0247 (2)0.0289 (3)
H8A0.41380.75450.02300.043*
H8B0.46930.8319−0.08600.043*
H8C0.45920.85290.11380.043*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.03424 (10)0.01869 (9)0.04038 (11)−0.00163 (6)−0.00389 (8)0.00074 (7)
N10.0244 (6)0.0181 (6)0.0259 (6)0.0005 (5)0.0057 (5)0.0004 (5)
C10.0236 (7)0.0204 (7)0.0261 (7)0.0020 (6)−0.0017 (6)0.0031 (6)
C20.0238 (8)0.0320 (9)0.0324 (8)0.0002 (7)0.0023 (6)0.0113 (7)
C30.0296 (9)0.0395 (11)0.0293 (8)0.0076 (8)0.0100 (7)0.0063 (7)
C40.0337 (9)0.0305 (9)0.0295 (8)0.0078 (7)0.0072 (7)−0.0017 (7)
C50.0264 (8)0.0220 (7)0.0275 (7)0.0016 (6)0.0042 (6)−0.0004 (6)
C60.0216 (7)0.0203 (7)0.0208 (6)0.0029 (6)0.0005 (5)0.0016 (5)
C70.0204 (7)0.0188 (7)0.0222 (6)0.0006 (5)0.0004 (5)−0.0031 (5)
C80.0255 (8)0.0368 (9)0.0244 (7)0.0091 (7)−0.0007 (6)0.0003 (6)

Geometric parameters (Å, °)

Br1—C11.9027 (16)C4—C51.389 (2)
N1—C71.2812 (19)C4—H4A0.9300
N1—N1i1.398 (2)C5—C61.396 (2)
C1—C21.389 (2)C5—H5A0.9300
C1—C61.393 (2)C6—C71.491 (2)
C2—C31.390 (3)C7—C81.499 (2)
C2—H2A0.9300C8—H8A0.9600
C3—C41.382 (3)C8—H8B0.9600
C3—H3A0.9300C8—H8C0.9600
C7—N1—N1i116.45 (14)C4—C5—H5A119.5
C2—C1—C6121.93 (16)C6—C5—H5A119.5
C2—C1—Br1118.05 (13)C1—C6—C5117.65 (14)
C6—C1—Br1119.97 (12)C1—C6—C7123.27 (14)
C1—C2—C3119.09 (16)C5—C6—C7119.08 (14)
C1—C2—H2A120.5N1—C7—C6115.40 (14)
C3—C2—H2A120.5N1—C7—C8124.31 (14)
C4—C3—C2120.19 (16)C6—C7—C8120.22 (13)
C4—C3—H3A119.9C7—C8—H8A109.5
C2—C3—H3A119.9C7—C8—H8B109.5
C3—C4—C5120.05 (17)H8A—C8—H8B109.5
C3—C4—H4A120.0C7—C8—H8C109.5
C5—C4—H4A120.0H8A—C8—H8C109.5
C4—C5—C6121.08 (16)H8B—C8—H8C109.5
C6—C1—C2—C30.8 (2)C4—C5—C6—C10.1 (2)
Br1—C1—C2—C3178.28 (13)C4—C5—C6—C7−179.65 (16)
C1—C2—C3—C4−0.3 (3)N1i—N1—C7—C6−173.12 (13)
C2—C3—C4—C5−0.2 (3)N1i—N1—C7—C83.8 (2)
C3—C4—C5—C60.3 (3)C1—C6—C7—N1−117.18 (17)
C2—C1—C6—C5−0.7 (2)C5—C6—C7—N162.6 (2)
Br1—C1—C6—C5−178.13 (12)C1—C6—C7—C865.7 (2)
C2—C1—C6—C7179.07 (15)C5—C6—C7—C8−114.47 (18)
Br1—C1—C6—C71.7 (2)

Symmetry codes: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
C3—H3A···Cg1ii0.932.833.7246 (17)161
C8—H8A···Cg1iii0.962.933.4989 (18)119

Symmetry codes: (ii) x+1, −y, z−3/2; (iii) x+3/2, −y, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: IS2578).

References

  • Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
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  • Cosier, J. & Glazer, A. M. (1986). J. Appl. Cryst.19, 105–107.
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