(E)-N′-(3-Bromo-5-chloro-2-hy­droxy­benzyl­idene)nicotinohydrazide

M Prabhu; K Parthipan; A Ramu; G Chakkaravarthi; G Rajagopal

doi:10.1107/S1600536811038268

. 2011 Sep 30;67(Pt 10):o2716. doi: 10.1107/S1600536811038268

(E)-N′-(3-Bromo-5-chloro-2-hydroxybenzylidene)nicotinohydrazide

M Prabhu ^a, K Parthipan ^b, A Ramu ^c, G Chakkaravarthi ^d,^*, G Rajagopal ^e,^*

PMCID: PMC3201283 PMID: 22065830

Abstract

There are two independent molecules in the asymmetric unit of the title compound, C₁₃H₉BrClN₃O₂, in which the dihedral angles between the benzene and pyridine rings are 8.23 (9)° and 52.84 (12)°. Both the molecules exist in an E configuration with respect to the C=N double bond. The two molecules in the asymmetric unit are linked via weak C—H⋯O hydrogen bonds. In both the molecules, an intramolecular O—H⋯N hydrogen bond generate an S(6) graph-set motif. In the crystal, intermolecular N—H⋯O and C—H⋯O hydrogen bonds generate bifurcated R ¹ ₂(7) ring motifs. The crystal packing is further stabilized by weak intermolecular N—H⋯O, N—H⋯N, C—H⋯O and π–π [centroid–centroid distance 3.615 (2) Å] interactions.

Related literature

For related structures, see: Naveenkumar et al. (2010 ▶); Su et al. (2010 ▶); Tecer et al. (2010 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₃H₉BrClN₃O₂
M _r = 354.59
Monoclinic,
a = 18.2217 (5) Å
b = 7.4666 (2) Å
c = 23.6916 (5) Å
β = 122.685 (1)°
V = 2712.93 (12) Å³
Z = 8
Mo Kα radiation
μ = 3.23 mm⁻¹
T = 295 K
0.30 × 0.24 × 0.20 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.444, T _max = 0.564
34991 measured reflections
8116 independent reflections
4715 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.125
S = 1.02
8116 reflections
377 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.27 e Å⁻³
Δρ_min = −0.84 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811038268/ng5231sup1.cif

e-67-o2716-sup1.cif^{(31.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811038268/ng5231Isup2.hkl

e-67-o2716-Isup2.hkl^{(389KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811038268/ng5231Isup3.cml

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
O2—H2B⋯N3	0.81 (1)	1.89 (3)	2.576 (3)	142 (4)
O4—H4A⋯N6	0.82 (1)	1.83 (2)	2.569 (3)	149 (4)
C15—H15⋯O2	0.93	2.55	3.286 (4)	137
C16—H16⋯O1	0.93	2.41	3.185 (4)	141
N2—H2A⋯O3ⁱ	0.85 (1)	2.06 (1)	2.906 (3)	171 (3)
C2—H2⋯O3ⁱ	0.93	2.52	3.380 (4)	153
N5—H5A⋯N1ⁱⁱ	0.86 (1)	2.16 (1)	3.009 (4)	170 (3)

Open in a new tab

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

Acknowledgments

The authors wish to acknowledge the SAIF, IIT, Madras, for the data collection.

supplementary crystallographic information

Comment

The geometric parameters of the title compound (I), agree well with the reported similar structures (Naveenkumar et al., 2010; Su et al., 2010; Tecer et al., 2010). The dihedral angles between the (C1/C2/N1/C3/C4/C5) and (C8-C13) is 8.23 (9)° and (C14/C15/C16/C17/N4/C18) and (C21-C26) is 52.84 (12)°. Both the molecules exist in an E configuration with respect to the C=N double bond. The two molecules in the asymmetric unit are linked via weak C15-H15···O2 and C16-H16···O1 hydrogen bonds. In both the molecules, the intramolecular O2-H2B···N3 and O4-H4A···N6 hydrogen bonds generate six-membered rings, each with graph-set motif S(6) (see, Fig. 1).

In the crystal structure (Fig. 2), the intermolecular N2-H2A···O3 and C2-H2···O3 hydrogen bonds generates a seven-membered ring, with bifurcated R¹₂(7) ring motif. The crystal packing is further stabilized due to weak intermolecular N-H···N, N-H···O, C-H···O (Table 1 ) and π···π [Cg4···Cg4 (2-x,1-y,1-z) = 3.614 (2)Å; Cg4 is the centroid of the ring (C21-C26)] interactions.

Experimental

Nicotinoylhydrazide (5 mmol) was dissolved in 20 mL of dry methanol with stirring and warming over a period of 10 min. To the warm hydrazide solution, 3- bromo-5-chloro salicylaldehyde (5 mmol) in 20 mL of dry methanol was added and the mixture was stirred and slowly refluxed for 2 h. The mixture was then cooled down to room temperature when pale yellow crystalline compound precipitated. The compound was collected by filtration, washed well with cold methanol and dried in vacuum. Single crystals suitable for the X-ray diffraction were obtained by slow evaporation of a solution of the title compound in methanol at room temperature. Melting Point: 503 K.