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Acta Crystallogr Sect E Struct Rep Online. 2010 July 1; 66(Pt 7): o1561.
Published online 2010 June 5. doi:  10.1107/S160053681001932X
PMCID: PMC3006706

2,3-Dimethyl-N-[(E)-4-nitro­benzyl­idene]aniline

Abstract

In the title compound, C15H14N2O2, the aromatic rings are oriented at a dihedral angle of 24.52 (5)°. The dihedral angle between the nitro group and its parent benzene ring is 9.22 (16)°. In the crystal, mol­ecules inter­act through aromatic π—π stacking inter­actions [centroid–centroid separations = 3.8158 (14) and 3.9139 (14) Å].

Related literature

For structural systematics of related compounds, see: Harada et al. (2004 [triangle]).

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Object name is e-66-o1561-scheme1.jpg

Experimental

Crystal data

  • C15H14N2O2
  • M r = 254.28
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1561-efi1.jpg
  • a = 7.1969 (5) Å
  • b = 11.8023 (7) Å
  • c = 15.3721 (8) Å
  • V = 1305.71 (14) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.09 mm−1
  • T = 296 K
  • 0.32 × 0.14 × 0.14 mm

Data collection

  • Bruker Kappa APEXII CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 2005 [triangle]) T min = 0.986, T max = 0.987
  • 13172 measured reflections
  • 1917 independent reflections
  • 1253 reflections with I > 2σ(I)
  • R int = 0.057

Refinement

  • R[F 2 > 2σ(F 2)] = 0.047
  • wR(F 2) = 0.111
  • S = 1.02
  • 1917 reflections
  • 174 parameters
  • H-atom parameters constrained
  • Δρmax = 0.12 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and PLATON (Spek, 2009 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]) and PLATON.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001932X/hb5464sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681001932X/hb5464Isup2.hkl

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

Acknowledgments

The authors acknowledge the provision of funds for the purchase of diffractometer and encouragement by Dr Muhammad Akram Chaudhary, Vice Chancellor, University of Sargodha, Pakistan.

supplementary crystallographic information

Comment

Torsional, vibration and central bond length of N-benzylideneanilines (Harada et al., 2004) has been studied for seven compounds at different temperatures. The title compound (I, Fig. 1) is another example due to change of substitutions at both phenyl rings for which the same study can be undertaken. The title compound has been prepared for derivatization.

The molecules of (I) are essentially monomeric having no intra or inter-molecular H-bondings. The phenyl rings A (C1—C6) and B (C10—C15) are planar with r. m. s. deviation of 0.0065 and 0.0022 Å respectively. The dihedral angle between A/B is 24.52 (5)°. The nitro group C (O1/N2/O2) is oriented at 9.22 (16)° with the parent phenyl ring. It is to be noted that the nitro substituated phenyl ring B has smaller bond lengths [1.365 (3)–1.387 (3) Å], whereas the 2,3-dimethyl substituated ring has longer bond lengths 1.373 (3)—1.401 (3) Å. The value of C═N bond length at room temperature for (I) is 1.262 (3) Å which is in compatible with the studies of Harada et al., 2004. The molecules are stabilized due to π—π interactions between the centroids of phenyl rings with separation of 3.8158 (14) and 3.9139 (14) Å.

Experimental

Equimolar quantities of 2,3-dimethylaniline and 4-nitro benzaldehyde were refluxed in methanol for 15 minutes resulting in yellow color precipitates. The contents of the flask were dried at room temperature and washed with methanol and ethanol, respectively. The washed crude material affoarded yellow needles of (I) in the solution of diethyl ether at room temperature by slow evaporation after 24 h.

Refinement

In the absence of anomalous scattering, all Friedal pairs were merged. Although all H-atoms were appeared in Fourier difference map but positioned geometrically (C–H = 0.93–0.96 Å) and refined as riding with Uiso(H) = xUeq(C), where x =1.2 for aryl C–H and x = 1.5 methyl H-atoms.

Figures

Fig. 1.
View of (I) with displacement ellipsoids drawn at the 50% probability level.

Crystal data

C15H14N2O2F(000) = 536
Mr = 254.28Dx = 1.294 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 1334 reflections
a = 7.1969 (5) Åθ = 2.1–25.4°
b = 11.8023 (7) ŵ = 0.09 mm1
c = 15.3721 (8) ÅT = 296 K
V = 1305.71 (14) Å3Needle, yellow
Z = 40.32 × 0.14 × 0.14 mm

Data collection

Bruker Kappa APEXII CCD diffractometer1917 independent reflections
Radiation source: fine-focus sealed tube1253 reflections with I > 2σ(I)
graphiteRint = 0.057
Detector resolution: 7.40 pixels mm-1θmax = 28.6°, θmin = 2.2°
ω scansh = −8→9
Absorption correction: multi-scan (SADABS; Bruker, 2005)k = −15→15
Tmin = 0.986, Tmax = 0.987l = −20→20
13172 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.047Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.111H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0482P)2 + 0.0883P] where P = (Fo2 + 2Fc2)/3
1917 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 0.12 e Å3
0 restraintsΔρmin = −0.14 e Å3

Special details

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles
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
O10.1409 (4)−0.19301 (18)0.70198 (14)0.0997 (9)
O20.1083 (4)−0.06237 (19)0.79842 (12)0.0941 (9)
N10.1128 (3)0.34130 (16)0.47092 (11)0.0485 (7)
N20.1253 (3)−0.0943 (2)0.72311 (16)0.0684 (9)
C10.1231 (3)0.42218 (18)0.40278 (13)0.0457 (7)
C20.1509 (3)0.5351 (2)0.42653 (14)0.0488 (8)
C30.1581 (4)0.61833 (19)0.36160 (15)0.0549 (8)
C40.1353 (4)0.5864 (2)0.27595 (17)0.0624 (10)
C50.1052 (4)0.4755 (2)0.25272 (16)0.0650 (10)
C60.0972 (4)0.3935 (2)0.31593 (14)0.0550 (8)
C70.1768 (4)0.5654 (2)0.52133 (14)0.0679 (10)
C80.1878 (5)0.7409 (2)0.38401 (19)0.0820 (13)
C90.1573 (4)0.23940 (19)0.45751 (14)0.0495 (8)
C100.1434 (3)0.15342 (18)0.52625 (14)0.0448 (7)
C110.1832 (3)0.04156 (19)0.50760 (15)0.0525 (8)
C120.1753 (4)−0.0397 (2)0.57139 (15)0.0551 (9)
C130.1287 (3)−0.0075 (2)0.65402 (14)0.0500 (8)
C140.0878 (3)0.1021 (2)0.67504 (15)0.0523 (8)
C150.0953 (3)0.18289 (19)0.61064 (14)0.0496 (8)
H40.140390.641450.232740.0748*
H50.090270.456170.194500.0779*
H60.074480.318540.300590.0659*
H7A0.091120.624290.536960.1016*
H7B0.301670.591280.530590.1016*
H7C0.153990.499720.556630.1016*
H8A0.184330.785580.331840.1229*
H8B0.306550.749810.411660.1229*
H8C0.091610.765710.422850.1229*
H90.200070.218220.402780.0594*
H110.215720.021050.451200.0630*
H120.20116−0.115090.558670.0661*
H140.055430.121650.731650.0627*
H150.068020.257970.623820.0596*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.131 (2)0.0586 (12)0.1094 (16)0.0005 (15)0.0004 (17)0.0307 (12)
O20.1205 (19)0.1055 (16)0.0563 (11)−0.0025 (15)−0.0044 (13)0.0275 (12)
N10.0509 (12)0.0484 (11)0.0463 (11)0.0052 (10)0.0029 (10)0.0042 (9)
N20.0614 (15)0.0707 (16)0.0731 (16)−0.0068 (14)−0.0072 (13)0.0266 (13)
C10.0431 (14)0.0477 (12)0.0463 (12)0.0035 (11)0.0067 (11)0.0043 (10)
C20.0454 (15)0.0529 (13)0.0482 (12)0.0020 (12)0.0069 (11)0.0015 (11)
C30.0515 (16)0.0504 (13)0.0628 (15)0.0051 (12)0.0070 (12)0.0082 (11)
C40.0660 (19)0.0615 (16)0.0596 (16)0.0045 (15)0.0068 (14)0.0193 (13)
C50.079 (2)0.0708 (17)0.0453 (12)0.0029 (16)0.0008 (14)0.0040 (12)
C60.0614 (16)0.0526 (14)0.0509 (14)0.0027 (13)0.0009 (13)−0.0010 (12)
C70.081 (2)0.0651 (16)0.0577 (14)−0.0020 (16)0.0041 (14)−0.0097 (13)
C80.105 (3)0.0539 (15)0.087 (2)−0.0044 (18)0.009 (2)0.0079 (15)
C90.0467 (15)0.0539 (13)0.0479 (12)0.0039 (12)0.0081 (12)0.0010 (11)
C100.0406 (13)0.0467 (12)0.0471 (13)0.0009 (11)0.0030 (11)0.0026 (10)
C110.0578 (16)0.0514 (13)0.0483 (12)0.0057 (12)0.0043 (11)−0.0031 (11)
C120.0608 (17)0.0424 (12)0.0621 (15)0.0015 (12)0.0011 (13)0.0007 (11)
C130.0436 (14)0.0550 (14)0.0515 (12)−0.0029 (12)−0.0050 (12)0.0116 (11)
C140.0521 (15)0.0601 (16)0.0447 (12)0.0018 (13)−0.0007 (11)0.0014 (12)
C150.0521 (15)0.0456 (12)0.0512 (13)0.0046 (12)0.0015 (12)0.0005 (11)

Geometric parameters (Å, °)

O1—N21.215 (3)C12—C131.368 (3)
O2—N21.224 (3)C13—C141.365 (3)
N1—C11.419 (3)C14—C151.376 (3)
N1—C91.262 (3)C4—H40.9300
N2—C131.476 (3)C5—H50.9300
C1—C21.396 (3)C6—H60.9300
C1—C61.390 (3)C7—H7A0.9600
C2—C31.401 (3)C7—H7B0.9600
C2—C71.512 (3)C7—H7C0.9600
C3—C41.379 (3)C8—H8A0.9600
C3—C81.502 (3)C8—H8B0.9600
C4—C51.374 (3)C8—H8C0.9600
C5—C61.373 (3)C9—H90.9300
C9—C101.468 (3)C11—H110.9300
C10—C111.381 (3)C12—H120.9300
C10—C151.387 (3)C14—H140.9300
C11—C121.373 (3)C15—H150.9300
C1—N1—C9120.49 (18)C5—C4—H4119.00
O1—N2—O2123.9 (2)C4—C5—H5120.00
O1—N2—C13118.2 (2)C6—C5—H5120.00
O2—N2—C13118.0 (2)C1—C6—H6120.00
N1—C1—C2117.16 (18)C5—C6—H6120.00
N1—C1—C6122.56 (19)C2—C7—H7A109.00
C2—C1—C6120.2 (2)C2—C7—H7B109.00
C1—C2—C3119.2 (2)C2—C7—H7C109.00
C1—C2—C7119.7 (2)H7A—C7—H7B110.00
C3—C2—C7121.1 (2)H7A—C7—H7C109.00
C2—C3—C4118.9 (2)H7B—C7—H7C109.00
C2—C3—C8121.1 (2)C3—C8—H8A109.00
C4—C3—C8119.9 (2)C3—C8—H8B109.00
C3—C4—C5121.8 (2)C3—C8—H8C109.00
C4—C5—C6119.6 (2)H8A—C8—H8B109.00
C1—C6—C5120.2 (2)H8A—C8—H8C109.00
N1—C9—C10121.6 (2)H8B—C8—H8C109.00
C9—C10—C11119.8 (2)N1—C9—H9119.00
C9—C10—C15121.1 (2)C10—C9—H9119.00
C11—C10—C15119.1 (2)C10—C11—H11120.00
C10—C11—C12120.7 (2)C12—C11—H11120.00
C11—C12—C13118.7 (2)C11—C12—H12121.00
N2—C13—C12118.7 (2)C13—C12—H12121.00
N2—C13—C14118.9 (2)C13—C14—H14121.00
C12—C13—C14122.4 (2)C15—C14—H14121.00
C13—C14—C15118.6 (2)C10—C15—H15120.00
C10—C15—C14120.6 (2)C14—C15—H15120.00
C3—C4—H4119.00
C9—N1—C1—C2−153.3 (2)C2—C3—C4—C50.2 (4)
C9—N1—C1—C630.1 (4)C8—C3—C4—C5−179.1 (3)
C1—N1—C9—C10−178.4 (2)C3—C4—C5—C60.1 (4)
O1—N2—C13—C12−9.2 (3)C4—C5—C6—C1−1.3 (4)
O1—N2—C13—C14171.7 (2)N1—C9—C10—C11176.3 (2)
O2—N2—C13—C12170.3 (3)N1—C9—C10—C15−5.4 (4)
O2—N2—C13—C14−8.8 (3)C9—C10—C11—C12178.5 (2)
N1—C1—C2—C3−178.7 (2)C15—C10—C11—C120.1 (3)
N1—C1—C2—C72.6 (3)C9—C10—C15—C14−178.2 (2)
C6—C1—C2—C3−2.0 (3)C11—C10—C15—C140.2 (3)
C6—C1—C2—C7179.3 (2)C10—C11—C12—C13−0.5 (4)
N1—C1—C6—C5178.8 (2)C11—C12—C13—N2−178.3 (2)
C2—C1—C6—C52.3 (4)C11—C12—C13—C140.8 (4)
C1—C2—C3—C40.8 (4)N2—C13—C14—C15178.6 (2)
C1—C2—C3—C8−180.0 (3)C12—C13—C14—C15−0.5 (3)
C7—C2—C3—C4179.4 (2)C13—C14—C15—C100.0 (3)
C7—C2—C3—C8−1.3 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5464).

References

  • Bruker (2005). SADABS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Harada, J., Harakawa, M. & Ogawa, K. (2004). Acta Cryst. B60, 578–588. [PubMed]
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Spek, A. L. (2009). Acta Cryst. D65, 148–155. [PMC free article] [PubMed]

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