1-[(Bromo­meth­yl)(phen­yl)meth­ylene]-2-(2,4-dinitro­phen­yl)hydrazine

Abdussalam Salhin; Norfarhah Abdul Razak; I A Rahman

doi:10.1107/S1600536809016225

. 2009 May 7;65(Pt 6):o1221–o1222. doi: 10.1107/S1600536809016225

1-[(Bromomethyl)(phenyl)methylene]-2-(2,4-dinitrophenyl)hydrazine

Abdussalam Salhin ^a,^*, Norfarhah Abdul Razak ^a, I A Rahman ^a

PMCID: PMC2969738 PMID: 21583090

Abstract

The title compound, C₁₄H₁₁BrN₄O₄, comprises two crystallographically independent molecules (A and B) in the asymmetric unit. In molecule B, intramolecular bifurcated N—H⋯O and N—H⋯Br hydrogen bonds and in molecule A, an intramolecular N—H⋯O hydrogen bond generate S(6) ring motifs. The dihedral angle between the phenyl and benzene rings is 5.44 (6) in molecule A and 7.63 (6)° in molecule B. The ortho- and meta-nitro substituents make dihedral angles of 6.67 (15) and 2.26 (15)° to the attached benzene ring in molecule A and 6.37 (17) and 5.81 (16)° in molecule B. The Br atom in molecule B is disordered over two positions with a refined site-occupancy ratio of 0.61 (3):0.39 (3). Interesting features of the crystal structure are the short Br⋯N [3.257 (3)–3.294 (4) Å], Br⋯O [3.279 (3)–3.307 (4) Å] and O⋯O [2.9319 (16)–2.9995 (16) Å] contacts, which are shorter than the sum of the van der Waals radii of these atoms. The crystal structure is further stabilized by intermolecular C—H⋯O and π–π interactions [centroid–centroid distances = 3.6643 (8)–3.8514 (8) Å].

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures and bioactivity, see; for example: Salhin et al. (2007 ▶); Tameem et al. (2006 ▶, 2007 ▶, 2008 ▶); Rollas & Küçükgüzel (2007 ▶); Shao et al. (2008 ▶).

Experimental

Crystal data

C₁₄H₁₁BrN₄O₄
M _r = 379.18
Monoclinic,
a = 13.0803 (3) Å
b = 15.3626 (3) Å
c = 14.1512 (2) Å
β = 91.903 (1)°
V = 2842.08 (9) Å³
Z = 8
Mo Kα radiation
μ = 2.92 mm⁻¹
T = 100 K
0.59 × 0.34 × 0.33 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.238, T _max = 0.381
45788 measured reflections
11112 independent reflections
8666 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.077
S = 1.01
11112 reflections
433 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.35 e Å⁻³

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

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016225/at2763sup1.cif

e-65-o1221-sup1.cif^{(28KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016225/at2763Isup2.hkl

e-65-o1221-Isup2.hkl^{(543.4KB, 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
N2B—H1NB⋯Br1B	0.82 (2)	2.826 (19)	3.3764 (12)	126.2 (15)
N2B—H1NB⋯O1B	0.82 (2)	1.969 (19)	2.6159 (16)	135.1 (17)
N2A—H1NA⋯O1A	0.79 (2)	2.02 (2)	2.6120 (16)	131.8 (19)
C2B—H2BA⋯Br1Aⁱ	0.93	2.93	3.673 (3)	138
C14B—H14C⋯O1Aⁱ	0.97	2.49	3.3352 (17)	145
C14B—H14D⋯O3Aⁱⁱ	0.97	2.52	3.3745 (18)	147

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

Acknowledgments

We thank the Malysian Government and Universiti Sains Malaysia for the Science Fund grant No. 1001/229/PKIMIA/811055.

supplementary crystallographic information

Comment

In view of the importance of hydrazone derivatives in chemical and biological applications (Rollas & Küçükgüzel, 2007; Shao et al., 2008), a series of hydrazone derivatives has been prepared in our laboratory, from which several X-ray structures have been reported (Salhin et al., 2007; Tameem et al., 2006, 2007 and 2008).

The title compound, C₁₄H₁₁BrN₄O₄, comprises two crystallographically independent molecules (A, B) in the asymmetric unit. In molecule B, intramolecular bifurcated N—H···O and N—H···Br hydrogen bonds and in molecule A, an intramolecular N—H···O hydrogen bond generate S(6) ring motifs. The dihedral angle between the phenyl rings in molecules A and B are 5.44 (6) and 7.63 (6)°, respectively. The ortho and meta nitro-substituents make the dihedral angles of 6.67 (15) and 2.26 (15)° in molecule A and 6.37917) and 5.81 (16)° to the benzene ring they are attached. The bromine group was disordered over two positins with a refined site-occupancy ratio of 0.61 (3)/0.39 (3) in molecule B. The crystal structure is further stabilized by intermolecular C—H···O and π-π [Cg1··· Cg1ⁱⁱⁱ = 3.6643 (8) Å, (iii) 2 - x, -y, 1 - z; Cg1··· Cg4^iv = 3.7308 (8) Å, (iv) 1 - x, -y, 1 - z; Cg1···Cg2^iv = 3.7013 (8) Å; Cg2···Cg3^iv = 3.7012 (8) Å; Cg3···Cg4^v = 3.8514 (8) Å, (v) -x, -y, 2 - z: Cg1, Cg2, Cg3, Cg4 are the centroids of the C1A–C6A, C8A–C13A, C1B–C6B, and C8B–C13b rings].

The interesting features of the crystal structure are short Br1A···N4A^vi [3.257 (3), (vi) 3/2-x,1/2+y,1/2-z], Br1C···N4A^vi [3.294 (4) Å], Br1A···O3A^viii [3.279 (3), (viii) 3/2-x,-1/2+y,1/2-z], Br1C···O3A^vii [3.307 (4) Å], O2A···O3A^iv [2.9319 (16) Å], and O1A···O4B^vii [2.9995(160 Å, (vii) 1/2-x,1/2+y,3/2-z] contacts which are shorter than the sum of the van der Waals radii of these atoms.

Experimental

2,4-Dinitrophenylhydrazine (0.5 g, 2.5 mmol) was dissolved in ethanol (10 ml), and H₂SO₄ solution (98%, 1 ml) was added slowly with stirring. The solution was heated on a water bath for several minutes until it cleared. An ethanol solution (5 ml) of α-bromoacetophenone (0.5 g, 2.5 mmol) was dropped slowly into the above solution with continuous stirring. The mixture was heated for another 5 minutes on water bath. On cooling to room temperature, an orange precipitate was formed. Recrystallization from ethanol solution produced the crystals of the title compound.