(E)-1-(2,4-Dinitro­phen­yl)-2-(2-fluoro­benzyl­idene)hydrazine

Jerry P Jasinski; Adam N Braley; C S Chidan Kumar; H S Yathirajan; A N Mayekar

doi:10.1107/S1600536811014383

. 2011 Apr 22;67(Pt 5):o1200–o1201. doi: 10.1107/S1600536811014383

(E)-1-(2,4-Dinitrophenyl)-2-(2-fluorobenzylidene)hydrazine

Jerry P Jasinski ^a,^*, Adam N Braley ^a, C S Chidan Kumar ^b, H S Yathirajan ^b, A N Mayekar ^c

PMCID: PMC3089184 PMID: 21754502

Abstract

In the title compound, C₁₃H₉FN₄O₄, the dihedral angle between the mean planes of the two benzene rings of the nearly planar molecule is 6.6 (9)°. The dihedral angles between the mean planes of the benzene ring and its two attached nitro groups are 6.7 (7) and 7.2 (9)°. Crystal packing is stabilized by N—H⋯O hydrogen bonds, weak C—H⋯O and C—H⋯F intermolecular interactions and centroid–centroid π-ring stacking interactions.

Related literature

For Schiff base propeties, see: Liang (2007 ▶). For nonlinear optical and crystalline properties, see: Baughman et al. (2004 ▶). For DNA-damaging and mutagenic agents, see: Okabe et al. (1993 ▶). For related structures, see: Bolte & Dill (1998 ▶); Shan et al. (2002 ▶); Fan et al. (2004 ▶); Motherwell & Ramsay, (2007 ▶); Shi et al. (2008 ▶); Ji et al. (2010 ▶); Kia et al. (2009 ▶); Jasinski et al. (2010 ▶).

Experimental

Crystal data

C₁₃H₉FN₄O₄
M _r = 304.24
Triclinic,
a = 7.0961 (8) Å
b = 8.2714 (9) Å
c = 11.7230 (8) Å
α = 88.614 (7)°
β = 80.544 (8)°
γ = 71.368 (10)°
V = 642.86 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 173 K
0.20 × 0.18 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T _min = 0.967, T _max = 1.000
6346 measured reflections
3466 independent reflections
2802 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.143
S = 1.09
3466 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Oxford Diffraction, 2007 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014383/ng5151sup1.cif

e-67-o1200-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014383/ng5151Isup2.hkl

e-67-o1200-Isup2.hkl^{(169.5KB, 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
N2—H2A⋯O1	0.88	2.02	2.6317 (15)	126
N2—H2A⋯O1ⁱ	0.88	2.51	3.3424 (15)	158
C2—H2B⋯F1ⁱⁱ	0.95	2.45	3.3386 (17)	156
C3—H3A⋯O4ⁱⁱⁱ	0.95	2.48	3.3177 (19)	148
C5—H5A⋯O3^iv	0.95	2.43	3.2694 (17)	148

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

Table 2. Cg⋯Cg π-ring stacking interactions.

Cg1 and Cg2 are the centroids of rings C1–C6 and C8–C13, respectively.

CgI⋯CgJ	Cg⋯Cg (Å)	CgI_Perp (Å)	CgJ_Perp (Å)
Cg1⋯Cg2ⁱ	3.6916 (10)	−3.4632 (6)	3.3267 (5)
Cg2⋯Cg1ⁱⁱ	3.6916 (10)	3.3267 (5)	−3.4632 (6)

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Symmetry codes: (i) 1 + x, y, z; (ii) −1 + x, y, z.

Acknowledgments

CSCK and HSY thank the University of Mysore for research facilities. JPJ acknowledges the NSF–MRI program (grant No. CHE1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

Comment

Schiff bases and their complexes are widely used in the fields of biology, catalysis etc. (Liang, 2007). Especially, the dinitrophenyl hydrazones exhibit good nonlinear optical (NLO) and crystalline properties (Baughman et al., 2004) and are found to have versatile coordinating abilities towards different metal ions. In addition, some 2,4-dinitrophenyl hydrazone derivatives have been shown to be potentially DNA-damaging and mutagenic agents (Okabe et al., 1993). As a result of their significant molecular nonlinearities many x-ray structural studies of 2,4-dinitrophenylhydrazones have been reported. Among them, the most closely related structures are (E)-p-methoxy-acetophenone 2,4-dinitrophenylhydrazone (Bolte & Dill, 1998), acetophenone (2,4-dinitrophenyl)hydrazone (Shan et al., 2002), 3-chloroacetophenone 2,4-dintrophenyl- hydrazone (Fan et al., 2004), 2,4-dihydroxyacetophenone 2,4-dinitrophenylhydrazone (Baughman et al., 2004), syn-acetophenone (2,4-dinitrophenyl) hydrazone (Motherwell & Ramsay, 2007), 1-(2-chlorobenzylidene)-2-(2,4-dinitrophenyl)hydrazine (Shi et al., 2008), N-(2,4-dinitrophenyl)-N'-(1-p-tolylethylidene) hydrazine (Kia et al., 2009), N-(2,4-dinitrophenyl)-N'-(1-phenylethylidene)hydrazine (Ji et al., 2010) and (1E)-1-(3-bromophenyl)ethanone 2,4-dinitrophenylhydrazone (Jasinski et al., 2010). In view of the importance of 2,4-dinitrophenylhydrazones, this paper reports the crystal structure of the title compound, C₁₃H₉FN₄O₄, (I).

In the title compound the dihedral angle between the mean planes of the two benzene rings of a nearly planar molecule is 6.69°, (Fig. 2). The dihedral angle between the mean planes of the benzene ring and its two bonded nitro groups are 6.7 (7)° and 7.2 (9)°, respectively. Crystal packing is stabilized by N—H···O hydrogen bonds (Fig. 3), weak C—H···O intermolecular interactions and Cg—Cg π-ring stacking interactions (Table 2).

Experimental

A mixture of 2,4-dinitrophenylhydrazine (1.98 g) and 2-fluorobenzaldehyde (1.24 g) was dissolved in methanol and refluxed for about 6h. The precipitate formed was filtered, dried and recrystallized in ethlyacetate. X-ray quality crystals of the title compound (I), were obtained after three days by the slow evaporation of a 1:1 mixture of dimethylformamide and pyridine at room temperature. (mp: 502 - 505 K).