(E)-1-(2,4-Dinitro­phen­yl)-2-[1-(3-nitro­phen­yl)ethyl­idene]hydrazine

Hoong-Kun Fun; Suchada Chantrapromma; Boonlerd Nilwanna; Thawanrat Kobkeatthawin; Nawong Boonnak

doi:10.1107/S1600536812034812

. 2012 Aug 11;68(Pt 9):o2684–o2685. doi: 10.1107/S1600536812034812

(E)-1-(2,4-Dinitrophenyl)-2-[1-(3-nitrophenyl)ethylidene]hydrazine

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

PMCID: PMC3435706 PMID: 22969577

Abstract

In the asymmetric unit of the title compound, C₁₄H₁₁N₅O₆, there are three crystallographically independent molecules with similar conformations but some differences in bond angles. The molecules are slightly twisted with the dihedral angles between the benzene rings being 10.02 (14), 8.41 (15) and 1.40 (14)°. In each molecule, an intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked by weak C—H⋯O interactions into a three-dimensional network. π–π interactions with centroid–centroid distances of 3.5635 (17)–3.8273 (18) Å are observed.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For a related structure, see: Chantrapromma et al. (2011 ▶). For background to and the biological activity of hydrozones, see: Cui et al. (2010 ▶); Krishnamoorthy et al. (2011 ▶); Molyneux (2004 ▶); Raja et al. (2012 ▶); Sathyadevi et al. (2012 ▶). 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 = 7.3309 (2) Å
b = 38.3569 (8) Å
c = 16.8027 (4) Å
β = 115.158 (1)°
V = 4276.57 (18) Å³
Z = 12
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 100 K
0.49 × 0.10 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.940, T _max = 0.988
49752 measured reflections
12460 independent reflections
7719 reflections with I > 2σ(I)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.077
wR(F ²) = 0.159
S = 1.07
12460 reflections
679 parameters
H-atom parameters constrained
Δρ_max = 0.51 e Å⁻³
Δρ_min = −0.38 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/S1600536812034812/is5180sup1.cif

e-68-o2684-sup1.cif^{(51.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812034812/is5180Isup2.hkl

e-68-o2684-Isup2.hkl^{(609.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812034812/is5180Isup3.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—H1AA⋯O1A	0.88	1.98	2.615 (3)	128
N1B—H1BA⋯O1B	0.88	2.01	2.637 (3)	127
N1C—H1CA⋯O1C	0.88	1.98	2.617 (3)	129
C3A—H3AA⋯O2A ⁱ	0.95	2.44	3.320 (3)	154
C3B—H3BA⋯O2C ⁱⁱ	0.95	2.40	3.188 (3)	140
C3C—H3CA⋯O2B ⁱⁱⁱ	0.95	2.52	3.413 (3)	156
C14B—H14F⋯O4A ^iv	0.98	2.53	3.316 (4)	137
C14C—H14J⋯O4C ⁱⁱⁱ	0.98	2.54	3.253 (4)	129

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

Acknowledgments

BN and TK thank the Crystal Materials Research Unit, Prince of Songkla University, for financial support. NB thanks Prince of Songkla University for a postdoctoral fellowship. The authors thank 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

Considerable attentions have been devoted to hydrazones and their complexes which have been acknowledged to possess diverse biological properties as antibacterial, antifungal, anagesic, anti-inflammatory as well as antioxidant activities (Cui et al., 2010; Krishnamoorthy et al., 2011; Raja et al., 2012; Sathyadevi et al., 2012). In our on-going research on bioactivity of hydrazones, the title compound (I) was synthesized and evaluated for antioxidant activity by DPPH scavenging (Molyneux, 2004) and was found to be weakly active with 30% inhibition. It was also screened for antibacterial activity and found to be inactive. Herein we report the synthesis and crystal structure of (I).

In the asymmetric unit of (I), C₁₄H₁₁N₅O₆, there are three crystallographically independent molecules A, B and C with similar conformations but some differences in bond angles (Fig. 1). The molecular structure is slightly twisted with the dihedral angle between the two benzene rings being 10.02 (14), 8.41 (15) and 1.40 (14)° in molecule A, B and C, respectively. The central ethylidenehydrazine bridge is planar with the torsion angles N1–N2–C7–C14 = 2.6 (4), -3.1 (4) and -2.1 (3)° in molecules A, B and C, respectively. This central N1/N2/C7/C14 plane makes dihedral angles of 12.90 (18) and 20.11 (18)° with the 2,4-dinitro- and 3-nitro-substituted benzene rings, respectively in molecule A, whereas the corresponding values are 12.50 (18) and 20.51 (18)° in molecule B, and 11.70 (18) and 12.33 (18)° in molecule C. In all three molecules, the nitro group of 3-nitrophenyl are co-planar with their bound benzene rings with r.m.s. deviations of 0.079 (2), 0.030 (2) and 0.025 (3) Å in molecules A, B and C, respectively, for the nine non H-atoms (C8–C13/N5/O5–O6). In the 2,4-dinitrophenyl, the ortho-nitro group lies on the same plane with its bound benzene ring with r.m.s. deviations of 0.023 (2), 0.075 (2) and 0.025 (2) Å in molecules A, B and C, repectively, for the nine non H-atoms (C1–C6/N3/O1–O2), but the para-nitro group is deviated with the torsion angles O3–N4–C4–C3 = 19.8 (3)° and O4–N4–C4–C3 = -160.9 (2)° in molecule A whereas the corresponding values are -9.8 (4) and 170.6 (2)° in molecule B, and -21.0 (3) and 159.4 (2)° in molecule C. In each molecule, intramolecular N—H···O hydrogen bonds between the hydrazone-NH and the ortho-nitro group (Fig. 1 and Table 1) generate three S(6) ring motifs (Bernstein et al., 1995). The bond distances are in normal ranges (Allen et al., 1987) and are comparable with the related structure (Chantrapromma et al., 2011).

In the crystal structure (Fig. 2), the molecules are linked by C—H···O weak interactions (Table 1) into a three-dimensional network. π–π interactions were presented with the distances of Cg1···Cg6 = 3.5635 (17) Å, Cg2···Cg5 = 3.5650 (18) Å, Cg3···Cg4^v = 3.6544 (18) Å and Cg3···Cg4^vi = 3.8273 (18) Å [symmetry codes: (v) 1 - x, 2 - y, 2 - z; (vi) 2 - x, 2 - y, 2 - z]; Cg1, Cg2, Cg3, Cg4, Cg5 and Cg6 are the centroids of C1A–C6A, C8A–C13A, C1B–C6B, C8B–C13BA, C1C–C6C and C8C–C13C 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. 3-Nitroacetophenone (0.35 g, 2 mmol) in ethanol (10.00 ml) was then added to the solution with continuous stirring. The solution was refluxed for 1 hr yielding an 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. 507–508 K).