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

Jerry P Jasinski; Ray J Butcher; L P Suchitra; H S Yathirajan; B Narayana

doi:10.1107/S1600536809044869

. 2009 Oct 31;65(Pt 11):o2968–o2969. doi: 10.1107/S1600536809044869

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

Jerry P Jasinski ^a, Ray J Butcher ^b,^*, L P Suchitra ^c, H S Yathirajan ^c, B Narayana ^d

PMCID: PMC2971143 PMID: 21578539

Abstract

In the title compound, C₁₂H₁₅BrN₂O₂, the dihedral angle between the benzene ring and the mean plane of the amide grouping is 77.7 (8)°. In the crystal, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur, and the packing is further supported by C—H⋯O and C—H⋯Br interactions and weak π–π ring stacking interactions.

Related literature

Hydrazides and their corresponding Schiff bases are useful precursors in the synthesis of several heterocyclic systems, see: Narayana et al. (2005 ▶; 2005a ▶). For the biological activity of substituted hydrazides, see: Cajocorius et al. (1977 ▶). Hydrazides are intermediates in the production of many pharmaceutically important compounds, see: Liu et al. (2006 ▶). For related structures, see: Butcher et al. (2007 ▶); Hou (2009 ▶); Li & Ban (2009 ▶); Sarojini et al. (2007a ▶,b ▶,c ▶,d ▶). For the MOPAC AM1 calculations, see: Schmidt & Polik (2007 ▶).

Experimental

Crystal data

C₁₂H₁₅BrN₂O₂
M _r = 299.17
Monoclinic,
a = 8.0942 (1) Å
b = 14.2475 (2) Å
c = 11.2974 (2) Å
β = 91.1519 (13)°
V = 1302.58 (3) Å³
Z = 4
Cu Kα radiation
μ = 4.25 mm⁻¹
T = 200 K
0.56 × 0.47 × 0.35 mm

Data collection

Oxford Diffraction Gemini R CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.452, T _max = 1.000
7962 measured reflections
2577 independent reflections
2484 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.122
S = 1.07
2577 reflections
157 parameters
H-atom parameters constrained
Δρ_max = 0.73 e Å⁻³
Δρ_min = −1.07 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; 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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044869/ds2010sup1.cif

e-65-o2968-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809044869/ds2010Isup2.hkl

e-65-o2968-Isup2.hkl^{(126.6KB, hkl)}

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
C7—H7B⋯O2ⁱ	0.98	2.60	3.561 (4)	166
C10—H10A⋯Brⁱⁱ	0.98	3.07	3.949 (5)	151
C10—H10A⋯O2ⁱⁱⁱ	0.98	2.55	3.231 (4)	127
C11—H11A⋯O1^iv	0.99	2.55	3.373 (4)	141
N1—H1A⋯O2ⁱⁱⁱ	0.88	2.07	2.932 (3)	165

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

LPS thanks the University of Mysore for use of their research facilities under the MPhil programme in Chemistry for the year 2008–2009. RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

Hydrazides and the corresponding Schiff bases are useful precursors in the synthesis of several heterocyclic systems (Narayana et al. 2005; 2005a). Some substituted hydrazides are reported to exhibit carcinostatic activity against several types of tumors (Cajocorius et al. 1977) and also possess antimicrobial activity. It is also used as an intermediate in many pharmaceutically important compounds (Liu et al. 2006). In continuation with our studies on the structures of hydrazides and their Schiff bases (Sarojini et al. 2007a, 2007b, 2007c, 2007d; Butcher et al. 2007) a new Schiff base, (I), C₁₂H₁5BrN₂O₂, has been synthesized and its crystal structure is now reported.

In the title compound, C₁₂H₁5BrN₂O₂, (Fig. 1), the 2-bromo and 5-methoxy groups are in the plane of the benzene ring. The dihedral angle between the mean planes of the carbonyl group (–C6—C8(O2)—N1—N2-) and benzene ring is 77.7 (8)°. The C1—C6—C8—O2 and C1—C6—C8—N1 torsion angles (-101.1 (3)° & -103.7 (3)°) support this observation. Crystal packing is supported by a collection of intermediate N1—H1A—O2 (-x,-y + 2,-z + 1) intermolecular interactions (see Table 1) which produces a cooperative network of infinite O—H···O—H···O—H chains arranged diagonally along the (101) plane of the unit cell (Fig. 2). In addition, weak intermolecular C10—H10A···O2 (-x,-y + 2,-z + 1), C11—H11A···O1 (-x + 1, y - 1/2,-z + 1/2), C7—H7B···O2 (-x,-y + 2,-z) and C10—H10A···Br (x,-y + 3/2,z1/2) interactions (Table 1) along with Cg1···Cg1 π-π ring stacking interactions at 3.869 (1)Å (2 - x,1 - y,1 - z; slippage = 1.43 (2) Å, where Cg1 = C1—C6), collectively, slightly influence crystal packing in this crystalline environment.

After a MOPAC AM1 computational calculation (Schmidt, 2007), the dihedral angle between the mean planes of the carbonyl group (–C6—C8(O2)—N1—N2-) and benzene ring becomes 84.0 (8)°, significantly greater that the 77.7 (8)° seen in the crystal. This supports the observation of a collective action of the intermediate and weak hydrogen bond interactions along with weak intermolecular π-π stacking interactions which influence crystal packing stability.

Experimental

A mixture of 2-bromo-5-methoxybenzohydrazide (2.45 g, 0.01 mol) and ethyl methyl ketone(1.44 g, 0.02 mol) in 20 ml of ethanol containing a drop of dilute sulfuric acid was refluxed for about 2 h (Scheme 2). On cooling, the solid separated was filtered and recrystallized from ethyl methyl ketone. M.P.: 385 K. Analysis for C₁₂H₁₅BrN₂O₂: Found (Calculated): C: 48.14 (48.18); H: 5.02 (5.05%); N: 9.31 (9.36%).