(E)-1-[1-(3-Chloro­phen­yl)ethyl­idene]-2-(2,4-dinitro­phen­yl)hydrazine

Hoong-Kun Fun; Suchada Chantrapromma; Boonlerd Nilwanna; Chatchanok Karalai

doi:10.1107/S160053681200548X

. 2012 Feb 17;68(Pt 3):o704–o705. doi: 10.1107/S160053681200548X

(E)-1-[1-(3-Chlorophenyl)ethylidene]-2-(2,4-dinitrophenyl)hydrazine

Hoong-Kun Fun ^a,^*,^‡, Suchada Chantrapromma ^b,^§, Boonlerd Nilwanna ^b, Chatchanok Karalai ^b

PMCID: PMC3295481 PMID: 22412592

Abstract

There are two crystallographically independent molecules in the asymmetric unit of the title compound, C₁₄H₁₁ClN₄O₄, with the same E conformation about the C=N double bond. The molecules are approximately planar, with a dihedral angle between the benzene rings of 10.24 (12)° in one molecule and 4.73 (12)° in the other. In both molecules, the ortho-nitro groups of the 2,4-dinitrophenyl units are coplanar to their bound benzene rings, whereas the para-nitro groups are slightly twisted. In each molecule, intramolecular N—H⋯O hydrogen bonds generate S(6) ring motifs. In the crystal, molecules are linked by weak C—H⋯O interactions into sheets parallel to the (-102) plane. These sheets are stacked by π–π interactions, with centroid–centroid distances of 3.7008 (14) and 3.7459 (14) Å. A Cl⋯O short contact [3.111 (2) Å] is observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Chantrapromma et al. (2011 ▶); Fun et al. (2011 ▶, 2012 ▶); Nilwanna et al. (2011 ▶). For background to biological activities of hydrazones, see: Angelusiu et al. (2010 ▶); Cui et al. (2010 ▶); Gokce et al. (2009 ▶); Khan et al. (2007 ▶): Loncle et al. (2004 ▶); Wang et al. (2009 ▶).

Experimental

Crystal data

C₁₄H₁₁ClN₄O₄
M _r = 334.72
Monoclinic,
a = 13.4825 (13) Å
b = 15.1586 (15) Å
c = 16.1281 (12) Å
β = 116.815 (6)°
V = 2941.8 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 296 K
0.42 × 0.19 × 0.18 mm

Data collection

Bruker APEX DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.889, T _max = 0.951
32600 measured reflections
8629 independent reflections
4617 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.183
S = 1.01
8629 reflections
417 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 datablock(s) global, I. DOI: 10.1107/S160053681200548X/rz2707sup1.cif

e-68-0o704-sup1.cif^{(36.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681200548X/rz2707Isup2.hkl

e-68-0o704-Isup2.hkl^{(422.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681200548X/rz2707Isup3.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
N1A—H1NA⋯O1A	0.82	1.95	2.598 (2)	135
N1B—H1NB⋯O1B	0.86	1.86	2.589 (2)	141
C5A—H5A⋯O1Aⁱ	0.93	2.52	3.251 (3)	136
C5B—H5B⋯O1Bⁱⁱ	0.93	2.33	3.196 (3)	154
C11A—H11A⋯O3Bⁱⁱⁱ	0.93	2.55	3.402 (3)	153
C11B—H11B⋯O3A^iv	0.93	2.58	3.429 (3)	153

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

Acknowledgments

The authors thank the Prince of Songkla University for financial support through the Crystal Materials Research Unit. The authors also thank the Universiti Sains Malaysia for the Research University grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Hydrazones are known to be bioactive compounds with antibacterial, antifungal, antitumor, anti-inflammatory as well as antioxidant (Angelusiu et al., 2010; Cui et al., 2010; Gokce et al., 2009; Khan et al., 2007; Loncle et al., 2004; Wang et al., 2009) activities. Within our on-going research on the bioactivity of hydrazones, the title compound (I) was synthesized in order to study and compare its biological activity with other related compounds (Chantrapromma et al., 2011; Fun et al., 2011; 2012; Nilwanna et al., 2011). Herein we report the synthesis and crystal structure of (I).

There are two crystallographic independent molecules A and B in the asymmetric unit of (I) with differences in bond angles (Fig. 1). The molecular structure of (I) is nearly planar with the dihedral angle between the two benzene rings of 10.24 (12)° in molecule A and 4.73 (12)° in molecule B. The central ethylidenehydrazine bridge (N1/N2/C7/C14) is planar with the torsion angles N1–N2–C7–C14 = 0.8 (3) and 0.5 (3)° in molecules A and B, repectively. The mean plane through this central bridge makes dihedral angles of 6.36 (17) and 3.90 (18)° with the 2,4-dinitrophenyl and 3-chlorophenyl rings, respectively in molecule A whereas the corresponding values are 5.37 (15) and 0.90 (15)° in molecule B. In both molecules, the ortho-nitro group of the 2,4-dinitrophenyl is coplanar with the attached benzene ring with the r.m.s. deviation of 0.0164 (2) Å for the nine non H-atoms (C1–C6/N3/O1/O2), and torsion angles O1–N3–C2–C3 = 176.84 (18)° and O2–N3–C2–C3 = -1.9 (3)°, whereas the para-nitro group is slightly twisted with the torsion angles O3–N4–C4–C5 = 168.8 (2)° and O4–N4–C4–C5 = -11.5 (3)° in molecule A; the corresponding values are 0.0176 (2) Å, -177.77 (18), 3.6 (3), 171.1 (2) and -8.9 (4)° in molecule B. In each molecule, intramolecular N—H···O hydrogen bond (Fig.1 and Table 1) generates S(6) ring motifs (Bernstein et al., 1995) The bond distances agree with the literature values (Allen et al., 1987) and are comparable with the related structures (Chantrapromma et al., 2011; Fun et al., 2011; 2012; Nilwanna et al., 2011).

In the crystal packing (Fig. 2), the molecules are linked by weak C—H···O interactions (Table 1) into sheets parallel to the (-102) plane. These sheets are further stacked along the a axis by π–π interactions with distances of Cg₁···Cg₂^v = 3.7459 (14) Å and Cg₁···Cg₃^vi = 3.7008 (14) Å [symmetry codes (v) = x, 3/2-y, 1/2+z; (vi) = 2-x, 2-y, 2-z]; Cg₁, Cg₂ and Cg₃ are the centroids of C1A–C6A, C8A–C13A and C8B–C13B benzene rings, respectively. A Cl1B···O1Bⁱⁱ [3.111 (2) Å] short contact is observed.

Experimental

The title compound (I) was synthesized by dissolving 2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) in ethanol (10.00 ml) and H₂SO₄ (conc.) (98 %, 0.50 ml) was slowly added with stirring. 3-Chloroacetophenone (0.26 ml, 2 mmol) was then added to the solution with continuous stirring. The solution was stirred for 1 h yielding an orange solid, which was filtered off and washed with methanol. Orange block-shaped single crystals of the title compound suitable for X-ray structure determination were recrystalized from ethanol by slow evaporation of the solvent at room temperature over several days. M.p. 478-479 K.