N-(3-Nitro­benzyl­idene)aniline

Muhammad Zaheer; Zareen Akhter; Michael Bolte; Humaira M Siddiqi

doi:10.1107/S1600536808036970

. 2008 Nov 20;64(Pt 12):o2381–o2382. doi: 10.1107/S1600536808036970

N-(3-Nitrobenzylidene)aniline

Muhammad Zaheer ^a, Zareen Akhter ^a,^*, Michael Bolte ^b, Humaira M Siddiqi ^a

PMCID: PMC2960009 PMID: 21581353

Abstract

In the title compound, C₁₃H₁₀N₂O₂, a Schiff base derivative, the dihedral angle between the two aromatic rings is 31.58 (3)°. The C=N double bond is essentially coplanar with the nitrophenyl ring. The torsion angle of the imine double bond is 175.97 (13)°, indicating that the C=N double bond is in a trans configuration. The crystal structure is stabilized by C—H⋯O contacts and π–π interactions (centroid–centroid distances of 3.807 and 3.808Å).

Related literature

Choi et al. (2000 ▶) and Nakamura et al. (1999 ▶) discuss the use of Schiff bases in the reduction of thionyl chloride, while Maruyama et al. (1995 ▶) and Burrows et al. (1996 ▶) describe their use in degradation processes. Hodnett & Mooney (1970 ▶), Rajavel et al. (2008 ▶) and Yu et al. (2007 ▶) discuss antineoplastic, antibacterial and antifungal activities, respectively. Hartley et al. (2002 ▶), Torregrosa et al. (2005 ▶) and Naeimi et al. (2008 ▶) describe different synthetic routes towards Schiff bases. Landy (1989 ▶) describes their role in biological redox systems. Yoon et al. (1990 ▶) and Park et al. (1998 ▶) discuss properties of Schiff base complexes such as alkene epoxidation and oxygen absorption by cobalt(II) complexes. Flack (1983 ▶) discusses the Rogers’s parameter for the characterization of enantiomorphic-polar compounds.

Experimental

Crystal data

C₁₃H₁₀N₂O₂
M _r = 226.23
Orthorhombic,
a = 7.3177 (6) Å
b = 12.1022 (11) Å
c = 12.4672 (12) Å
V = 1104.10 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 173 (2) K
0.48 × 0.48 × 0.46 mm

Data collection

Stoe IPDSII two-circle diffractometer
Absorption correction: none
9868 measured reflections
1585 independent reflections
1421 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.093
S = 1.04
1585 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808036970/zl2143sup1.cif

e-64-o2381-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808036970/zl2143Isup2.hkl

e-64-o2381-Isup2.hkl^{(78.2KB, 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
C6—H6⋯O1ⁱ	0.95	2.70	3.261 (2)	118
C6—H6⋯O2ⁱⁱ	0.95	2.71	3.303 (2)	122
C7—H7⋯O1ⁱ	0.95	2.66	3.237 (2)	120
C13—H13⋯O2ⁱⁱⁱ	0.95	2.64	3.541 (2)	159

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

Acknowledgments

The authors are grateful to the Department of Chemistry, Quaid-I-Azam University, Islamabad, Pakistan and the Institute for Inorganic Chemistry, University of Frankfurt, Germany, for providing laboratory and analytical facility.

supplementary crystallographic information

Comment

Schiff bases and their complexes are widely studied because of their interesting and important properties such as their ability to reversibly bind oxygen (Park et al., 1998) and their use in catalysis. They are part of redox systems in biological systems (Landy, 1989), they are used in the degradation of dyes through decomposition of hydrogen peroxide and other reagents in the textile industry (Maruyama et al., 1995) as well as in the reduction of thionyl chloride (Choi et al., 2000; Nakamura et al., 1999). These compounds can also be used in the degradation of organic compounds (Burrows et al., 1996) and in radiopharmaceuticals (Yoon et al., 1990). Schiff bases also exhibit antineoplastic (Hodnett et al., 1970) antibacterial (Rajavel et al., 2008) and antifungal (Yu et al. 2007) activities. The compound whose crystal structure is reported was synthesized for comparative studies of the biological applications of Schiff bases with and without a ferrocene moiety. The synthesis of the present compound was reported earlier by Torregrosa (Torregrosa et al., 2005), Hartley (Hartley et al., 2002) and Naeimi (Naeimi et al., 2008). We have utilized a different modified method for the synthesis of this compound as described below.

Geometric parameters of the title compound (Fig. 1) are in the usual ranges. The molecule is composed of two almost planar moieties, the 3-nitrobenzylidene moieties and the phenyl ring. The dihedral angle between the two aromatic rings is 31.58 (3)°. The torsion angle C11-N1-C1-C2 [175.97 (13)°] shows that the C-N double bond is trans configured. The crystal packing (Fig. 2) is stabilized by some short C-H···O contacts (see Table 1) and π–π stacking interactions (cog_phenyl···cog_nitrophenylⁱ = 3.807Å, cog_phenyl···cog_nitrophenylⁱⁱ = 3.808Å; symmetry operators: (i) -1/2+x, 3/2-y, 1-z; (ii) 1/2+x, 3/2-y, 1-z).

Experimental

In a 250 ml pre-backed two neck flask supplied with a magnetic stirrer, 4 ml (43 mmol) of freshly distilled aniline was mixed with 4.97 g (43 mmol) of 3-nitrobenzaldehyde in dry toluene as the solvent. The reaction mnixture was heated to reflux using a Dean and Stark apparatus for azeotropic removal of water formed during the reaction. Reaction progress was monitored using TLC and the solid obtained after rotary evaporation was recrystallized from a mixture of ethyl acetate and n-hexane. Yield: 80%, melting point: 337-338K.