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

Suchada Chantrapromma; Boonlerd Nilwanna; Patcharaporn Jansrisewangwong; Thawanrat Kobkeatthawin; Hoong-Kun Fun

doi:10.1107/S160053681105001X

. 2011 Nov 30;67(Pt 12):o3499–o3500. doi: 10.1107/S160053681105001X

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

Suchada Chantrapromma ^a,^*,^‡, Boonlerd Nilwanna ^a, Patcharaporn Jansrisewangwong ^a, Thawanrat Kobkeatthawin ^a, Hoong-Kun Fun ^b,^§

PMCID: PMC3239123 PMID: 22199971

Abstract

The title molecule, C₁₄H₁₁ClN₄O₄, is in an E configuration and is twisted with the dihedral angle between the two benzene rings being 38.48 (8)°. The ethylidenehydrazine plane makes dihedral angles of 6.03 (10) and 44.04 (11)°, respectively, with the dinitro- and chloro-substituted benzene rings. The two nitro groups are essentially coplanar with the bound benzene ring, making dihedral angles of 0.9 (2) and 1.65 (18)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked by a weak C—H⋯O interaction into a chain along the c axis. The chains are further stacked along the b axis by a π–π interaction with a centroid–centroid distance of 3.6088 (10) Å.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For related structures, see: Fun et al. (2010 ▶, 2011 ▶); Jansrisewangwong et al. (2010 ▶); Nilwanna et al. (2011 ▶). For background to and the biological activity of hydrozones, see: Angelusiu et al. (2010 ▶); Bendre et al. (1998 ▶); Gokce et al. (2009 ▶); Li et al. (2008 ▶); Loncle et al. (2004 ▶).

Experimental

Crystal data

C₁₄H₁₁ClN₄O₄
M _r = 334.72
Monoclinic,
a = 32.660 (3) Å
b = 7.1435 (7) Å
c = 13.4798 (13) Å
β = 112.215 (2)°
V = 2911.5 (5) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 297 K
0.36 × 0.26 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.904, T _max = 0.957
16146 measured reflections
4458 independent reflections
3036 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.127
S = 1.04
4458 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.27 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/S160053681105001X/is5008sup1.cif

e-67-o3499-sup1.cif^{(19.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681105001X/is5008Isup2.hkl

e-67-o3499-Isup2.hkl^{(218.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681105001X/is5008Isup3.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
N2—H1N1⋯O1	0.85 (2)	1.97 (2)	2.6081 (19)	131.2 (17)
C6—H6A⋯O3ⁱ	0.93	2.52	3.251 (2)	135

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Symmetry code: (i) Inline graphic .

Acknowledgments

BN, PJ and TK thank the Crystal Materials Research Unit, Prince of Songkla University, for financial support. The authors also thank the Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Hydrazones have been known to be responsible for various bioactivities such as antibacterial (Angelusiu et al., 2010), antioxidant (Li et al., 2008), antifungal (Loncle et al., 2004), anti-inflammatory (Gokce et al., 2009) and also tyrosinase inhibitory (Bendre et al., 1998) activities. With our on-going research on medicinal chemistry, we previously reported the syntheses and crystal structures of some hydrazone derivatives (Fun et al., 2010, 2011; Jansrisewangwong et al., 2010; Nilwanna et al., 2011). Herein we report the crystal structure of the title compound. It was screened for antioxidant and antibacterial activities and found to be inactive.

The title molecule (Fig. 1), C₁₄H₁₁ClN₄O₄, is twisted and exists in an E configuration with respect to the ethylidene C7═N1 double bond [1.2877 (17) Å] with the torsion angle N2–N1–C7–C8 = -176.69 (13)°. The dihedral angle between the benzene rings of the 2,4-dinitrophenyl and 2-chlorophenyl groups is 38.48 (8)°. The middle ethylidenehydrazine unit (C7/C14/N1/N2) is planar with an r.m.s deviation of 0.0040 (1) Å and the torsion angle of N2–N1–C7–C14 is -1.3 (2)°. This middle C/C/N/N plane makes the dihedral angles of 6.03 (10) and 44.04 (11)° with the 2,4-dinitrophenyl and 2-chlorophenyl rings, respectively. The two nitro groups of 2,4-dinitrophenyl are essentially co-planar with the bound benzene ring with an r.m.s. deviation of 0.0081 (1) Å for the twelve non H-atoms and the O–N–C–C angles are -0.3 (2), 0.2 (2), 0.1 (3) and -0.1 (3)°. An intramolecular N—H···O hydrogen bond between the hydrazone-NH and the ortho nitro group (Fig. 1 and Table 1) generates an S(6) ring motif (Bernstein et al., 1995). The bond distances are within the normal range (Allen et al., 1987) and are comparable with related structures (Fun et al., 2010, 2011; Jansrisewangwong et al., 2010; Nilwanna et al., 2011).

In the crystal structure (Fig. 2), the molecules are linked by weak C—H···O interactions (Table 1) into chains along the c axis in a head-to-head manner. These chains are further stacked along the b axis by a π–π interaction with Cg1···Cg2ⁱⁱ distance of 3.6088 (10) Å [symmetry code: (ii) x, 1 - y, 1/2 + z]; Cg1 and Cg2 are the centroids of C1–C6 and C8–C13 benzene rings, respectively.

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. 2-Chloroacetophenone (0.30 ml, 2 mmol) was then added to the solution with continuous stirring. The solution was refluxed for 1 h yielding a yellow solid, which was filtered off and washed with methanol. Yellow block-shaped single crystals of the title compound suitable for X-ray diffraction were recrystalized from ethanol by slow evaporation of the solvent at room temperature over several days (m.p. 478–479).