(E)-1-(2,4-Dinitro­phen­yl)-2-[1-(2-nitro­phen­yl)ethyl­idene]hydrazine

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

doi:10.1107/S1600536811042620

. 2011 Oct 29;67(Pt 11):o3084–o3085. doi: 10.1107/S1600536811042620

(E)-1-(2,4-Dinitrophenyl)-2-[1-(2-nitrophenyl)ethylidene]hydrazine

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

PMCID: PMC3247472 PMID: 22220090

Abstract

The title compound, C₁₄H₁₁N₅O₆, was obtained from the condensation reaction of 2,4-dinitrophenylhydrazine and 2-nitroacetophenone. The molecule displays an E conformation about the C=N double bond and an intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. The dihedral angle between the benzene rings is 7.84 (6)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds and π–π stacking interactions [centroid–centroid distance = 3.6447 (8) Å] into a three-dimensional network.

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. (2011 ▶); Shan et al. (2003 ▶). For background to and the physiological and biological activity of hydrozones, see: Bendre et al. (1998 ▶); Nakamura & Goto (1996 ▶); Rollas & Küçükgüzel (2007 ▶); Singh et al. (2005 ▶); Yacorb (1999 ▶). For the stability of the temperature controller used in the data collection, see Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₄H₁₁N₅O₆
M _r = 345.28
Monoclinic,
a = 11.9313 (9) Å
b = 8.6700 (7) Å
c = 15.2363 (9) Å
β = 112.455 (5)°
V = 1456.61 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.40 × 0.16 × 0.13 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.951, T _max = 0.984
16360 measured reflections
4244 independent reflections
3361 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.110
S = 1.04
4244 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.28 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 datablock(s) global, I. DOI: 10.1107/S1600536811042620/rz2643sup1.cif

e-67-o3084-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811042620/rz2643Isup2.hkl

e-67-o3084-Isup2.hkl^{(208KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811042620/rz2643Isup3.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
N1—H1⋯O2	0.88	1.94	2.6026 (13)	131
C10—H10A⋯O4ⁱ	0.93	2.42	3.2313 (16)	146
C12—H12A⋯O4ⁱⁱ	0.93	2.55	3.4353 (18)	159

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

Acknowledgments

BN and PJ thank the Crystal Materials Research Unit, Prince of Songkla University, for financial support. The authors thank the Prince of Songkla University and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. Mr Teerasak Anantapong, Department of Biotechnology, Faculty of Agro-Industry, Prince of Songkla University, is acknowledged for the bacterial assay.

supplementary crystallographic information

Comment

Hydrazones exhibit physiological and biological activities in the treatment of several diseases with anticonvulsant, antidepressant, analgesic, antiinflammatory, antiplatelet, antimalarial, antimicrobial, antimycobacterial, antitumor, vasodilator, antiviral, antischistosomiasis (Singh et al., 2005; Rollas & Küçükgüzel, 2007) and tyrosinase inhibitory properties (Bendre et al., 1998). Furthermore, they were used in engineering and analytical studies for aldehydes and ketones sampling (Yacorb, 1999) and analysis of protein carbonyls (Nakamura & Goto, 1996). These interesting activities have led us to synthesize the title hydrazone derivative (I). It was screened for antioxidant and antibacterial activities. Our results found that (I) is inactive for these tests. Herein we report the synthesis and crystal structure of (I).

The whole molecule of (I) (Fig. 1), C₁₄H₁₁N₅O₆, is not planar and exists in an E configuration with respect to the ethylidene C═N double bond [1.2905 (15) Å] with the torsion angle N1–N2–C7–C8 = 177.22 (10)°. The dihedral angle between the two benzene rings is 7.84 (6)°. The middle ethylidenehydrazine fragment (C7/C14/N1/N2) is planar with the r.m.s deviation of 0.0047 (1) Å. This middle C/C/N/N plane makes the dihedral angles of 11.28 (8) and 9.78 (8)° with the C1–C6 and C8–C13 benzene rings, respectively. The two nitro groups of 2,4-dinitrophenyl are co-planar with the bound benzene ring with the r.m.s. deviation of 0.0369 (1) Å for the twelve non H-atoms. However the nitro group of the 2-nitrophenyl tilts away from its bound benzene ring with the dihedral angle of 81.19 (7)° between the C9/N5/O5/O6 plane and C8–C13 benzene ring. This orientation is caused by the steric interaction between the hydrazine and nitro group. An intramolecular N1—H1···O2 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 expected range (Allen et al., 1987) and are comparable with those of related structures (Fun et al., 2011; Shan et al., 2003).

In the crystal structure, the molecules are linked by weak C—H···O hydrogen bonds (Table 1) into a three-dimensional network (Fig. 2) enforced by π···π stacking interactions (Cg₁···Cg₂ⁱ = 3.6447 (8) Å; Cg₁ and Cg₂ are the centroids of C1–C6 and C8–C13 benzenre rings, respectively; symmetry code: (i) 2 - x, 2 - y, 1 - z). Short C···O (2.9999 (15) Å] contacts are also observed.

Experimental

The title compound was synthesized by dissolving 2,4-dinitrophenylhydrazine (0.40 g, 2 mmol) in ethanol (10.00 ml), and H₂SO₄ (98%, 0.50 ml) was slowly added with stirring. 2-Nitroacetophenone (0.27 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 structure determination were recrystalized from ethanol by slow evaporation of the solvent at room temperature over several days. M.p. 443–444 K.