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Acta Crystallogr Sect E Struct Rep Online. 2008 December 1; 64(Pt 12): o2381–o2382.
Published online 2008 November 20. doi:  10.1107/S1600536808036970
PMCID: PMC2960009

N-(3-Nitro­benzyl­idene)aniline

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

An external file that holds a picture, illustration, etc.
Object name is e-64-o2381-scheme1.jpg

Experimental

Crystal data

  • C13H10N2O2
  • M r = 226.23
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2381-efi1.jpg
  • 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
  • Δρmax = 0.26 e Å−3
  • Δρmin = −0.14 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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 (cogphenyl···cognitrophenyli = 3.807Å, cogphenyl···cognitrophenylii = 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.

Refinement

All H atoms could be located by difference Fourier synthesis. Nevertheless, they were refined with fixed individual isotropic displacement parameters [Uiso(H) = 1.2 Ueq(C)] using a riding model with C—H = 0.95 Å.

In the absence of anomalous scatterers, the Flack (1983) parameter is meaningless and therefore Friedel pairs were merged prior to refinement.

Figures

Fig. 1.
Perspective view of the title compound with the numbering scheme and displacement ellipsoids at the 50 % probability level. H atoms are drawn as spheres of arbitrary radii.
Fig. 2.
Packing diagram of the title compound with view onto the bc plane. Hydrogen bonds are shown as dashed lines.
Fig. 3.
Packing diagram of the title compound with view onto the ac plane. π–π stacking interactions are shown as dashed lines.

Crystal data

C13H10N2O2F000 = 472
Mr = 226.23Dx = 1.361 Mg m3
Orthorhombic, P212121Mo Kα radiation λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 7899 reflections
a = 7.3177 (6) Åθ = 3.7–25.8º
b = 12.1022 (11) ŵ = 0.09 mm1
c = 12.4672 (12) ÅT = 173 (2) K
V = 1104.10 (17) Å3Block, colourless
Z = 40.48 × 0.48 × 0.46 mm

Data collection

Stoe IPDSII two-circle diffractometer1421 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.054
Monochromator: graphiteθmax = 29.5º
T = 173(2) Kθmin = 3.6º
ω scansh = −9→8
Absorption correction: nonek = −16→14
9868 measured reflectionsl = −15→17
1585 independent reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.034H-atom parameters constrained
wR(F2) = 0.093  w = 1/[σ2(Fo2) + (0.0638P)2 + 0.081P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
1585 reflectionsΔρmax = 0.26 e Å3
154 parametersΔρmin = −0.14 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
N10.85150 (17)0.74236 (10)0.59232 (10)0.0265 (3)
N20.9518 (2)0.83182 (11)0.11436 (10)0.0339 (3)
O10.9459 (2)0.90457 (11)0.04548 (10)0.0507 (4)
O20.9936 (2)0.73588 (10)0.09536 (9)0.0525 (4)
C10.9027 (2)0.72475 (11)0.49536 (12)0.0255 (3)
H10.95300.65490.47710.031*
C20.8855 (2)0.81012 (11)0.41137 (12)0.0239 (3)
C30.9276 (2)0.78262 (11)0.30530 (11)0.0243 (3)
H30.96850.71040.28760.029*
C40.9088 (2)0.86252 (12)0.22632 (11)0.0262 (3)
C50.8499 (2)0.96943 (12)0.24807 (12)0.0296 (3)
H50.83831.02250.19240.036*
C60.8086 (2)0.99625 (12)0.35358 (13)0.0314 (4)
H60.76781.06870.37050.038*
C70.8262 (2)0.91791 (12)0.43499 (12)0.0277 (3)
H70.79790.93750.50690.033*
C110.86161 (19)0.65339 (11)0.66706 (11)0.0239 (3)
C120.9017 (2)0.67860 (12)0.77429 (12)0.0291 (3)
H120.92290.75310.79470.035*
C130.9105 (2)0.59535 (14)0.85102 (12)0.0337 (4)
H130.93990.61300.92320.040*
C140.8763 (2)0.48619 (13)0.82226 (13)0.0332 (4)
H140.88320.42920.87450.040*
C150.8317 (2)0.46086 (12)0.71627 (13)0.0308 (3)
H150.80620.38660.69680.037*
C160.8244 (2)0.54339 (12)0.63890 (12)0.0261 (3)
H160.79420.52530.56690.031*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0264 (6)0.0264 (6)0.0267 (6)−0.0005 (5)0.0001 (5)0.0030 (5)
N20.0391 (8)0.0365 (7)0.0262 (6)−0.0015 (6)−0.0042 (6)0.0052 (5)
O10.0677 (9)0.0548 (7)0.0297 (6)0.0073 (8)0.0022 (7)0.0184 (5)
O20.0883 (12)0.0392 (7)0.0301 (6)0.0053 (7)0.0001 (7)−0.0027 (5)
C10.0230 (7)0.0265 (7)0.0271 (7)0.0011 (6)−0.0012 (6)0.0032 (6)
C20.0210 (6)0.0249 (6)0.0259 (7)−0.0010 (5)−0.0021 (6)0.0033 (5)
C30.0227 (7)0.0242 (6)0.0261 (6)−0.0004 (5)−0.0030 (6)0.0026 (5)
C40.0255 (7)0.0278 (7)0.0255 (7)−0.0031 (6)−0.0027 (6)0.0043 (6)
C50.0279 (8)0.0267 (7)0.0342 (7)−0.0009 (6)−0.0048 (6)0.0093 (6)
C60.0304 (8)0.0239 (7)0.0399 (8)0.0012 (6)−0.0006 (7)0.0031 (6)
C70.0257 (7)0.0270 (7)0.0305 (7)0.0009 (6)0.0022 (6)0.0023 (6)
C110.0204 (6)0.0264 (6)0.0248 (7)0.0013 (5)0.0026 (6)0.0024 (6)
C120.0297 (8)0.0313 (7)0.0264 (7)0.0001 (6)0.0013 (6)−0.0029 (6)
C130.0351 (8)0.0439 (8)0.0222 (6)0.0014 (7)−0.0008 (7)0.0021 (6)
C140.0306 (8)0.0376 (8)0.0314 (7)0.0023 (6)0.0023 (6)0.0127 (7)
C150.0297 (8)0.0269 (7)0.0359 (8)−0.0003 (6)0.0037 (7)0.0032 (6)
C160.0252 (7)0.0283 (7)0.0247 (6)−0.0001 (6)0.0015 (6)−0.0001 (6)

Geometric parameters (Å, °)

N1—C11.283 (2)C6—C71.395 (2)
N1—C111.4258 (18)C6—H60.9500
N2—O21.2237 (18)C7—H70.9500
N2—O11.2306 (17)C11—C121.402 (2)
N2—C41.4783 (19)C11—C161.4034 (19)
C1—C21.476 (2)C12—C131.391 (2)
C1—H10.9500C12—H120.9500
C2—C31.398 (2)C13—C141.391 (2)
C2—C71.4060 (19)C13—H130.9500
C3—C41.3869 (19)C14—C151.395 (2)
C3—H30.9500C14—H140.9500
C4—C51.390 (2)C15—C161.390 (2)
C5—C61.388 (2)C15—H150.9500
C5—H50.9500C16—H160.9500
C1—N1—C11118.36 (12)C6—C7—C2120.45 (14)
O2—N2—O1123.54 (14)C6—C7—H7119.8
O2—N2—C4118.32 (12)C2—C7—H7119.8
O1—N2—C4118.14 (13)C12—C11—C16119.04 (13)
N1—C1—C2121.80 (13)C12—C11—N1118.00 (12)
N1—C1—H1119.1C16—C11—N1122.88 (13)
C2—C1—H1119.1C13—C12—C11120.52 (14)
C3—C2—C7119.15 (12)C13—C12—H12119.7
C3—C2—C1119.04 (12)C11—C12—H12119.7
C7—C2—C1121.81 (13)C12—C13—C14120.15 (14)
C4—C3—C2118.92 (13)C12—C13—H13119.9
C4—C3—H3120.5C14—C13—H13119.9
C2—C3—H3120.5C13—C14—C15119.65 (14)
C3—C4—C5122.76 (14)C13—C14—H14120.2
C3—C4—N2118.30 (13)C15—C14—H14120.2
C5—C4—N2118.94 (12)C16—C15—C14120.57 (14)
C6—C5—C4118.03 (13)C16—C15—H15119.7
C6—C5—H5121.0C14—C15—H15119.7
C4—C5—H5121.0C15—C16—C11120.04 (13)
C5—C6—C7120.69 (14)C15—C16—H16120.0
C5—C6—H6119.7C11—C16—H16120.0
C7—C6—H6119.7
C11—N1—C1—C2175.97 (13)C5—C6—C7—C2−0.3 (2)
N1—C1—C2—C3−174.08 (15)C3—C2—C7—C60.4 (2)
N1—C1—C2—C75.3 (2)C1—C2—C7—C6−179.00 (14)
C7—C2—C3—C4−0.3 (2)C1—N1—C11—C12146.81 (14)
C1—C2—C3—C4179.08 (12)C1—N1—C11—C16−36.5 (2)
C2—C3—C4—C50.1 (2)C16—C11—C12—C132.1 (2)
C2—C3—C4—N2−179.28 (15)N1—C11—C12—C13179.00 (13)
O2—N2—C4—C33.5 (2)C11—C12—C13—C14−1.1 (2)
O1—N2—C4—C3−175.59 (15)C12—C13—C14—C15−0.5 (2)
O2—N2—C4—C5−175.94 (16)C13—C14—C15—C161.1 (2)
O1—N2—C4—C55.0 (2)C14—C15—C16—C11−0.1 (2)
C3—C4—C5—C60.0 (2)C12—C11—C16—C15−1.5 (2)
N2—C4—C5—C6179.38 (14)N1—C11—C16—C15−178.20 (13)
C4—C5—C6—C70.1 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C6—H6···O1i0.952.703.261 (2)118
C6—H6···O2ii0.952.713.303 (2)122
C7—H7···O1i0.952.663.237 (2)120
C13—H13···O2iii0.952.643.541 (2)159

Symmetry codes: (i) −x+3/2, −y+2, z+1/2; (ii) −x+2, y+1/2, −z+1/2; (iii) x, y, z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: ZL2143).

References

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