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Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o78.
Published online 2007 December 6. doi:  10.1107/S1600536807061028
PMCID: PMC2915035

(6E)-N-[(4Z)-2,5-Dimethyl-4-(p-tolyl­imino)cyclo­hexa-2,5-dienyl­idene]-4-methyl­aniline

Abstract

The title compound, C22H22N2, was prepared by the reaction of 4-amino­toluene with sodium carbonate, sodium hydroxide and potassium permanganate. The mol­ecule is disposed about a crystallographic inversion centre with one half-mol­ecule comprising the asymmetric unit. The dihedral angle between the terminal and central benzene rings is 88.05 (1)°. The crystal packing is stabilized by van der Waals forces.

Related literature

For related literature, see: Boyer et al. (2000 [triangle]); Hadek (1968 [triangle]); Hadek et al. (1969 [triangle])

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Object name is e-64-00o78-scheme1.jpg

Experimental

Crystal data

  • C22H22N2
  • M r = 314.42
  • Trigonal, An external file that holds a picture, illustration, etc.
Object name is e-64-00o78-efi4.jpg
  • a = 21.173 (8) Å
  • c = 10.476 (2) Å
  • V = 4067 (2) Å3
  • Z = 9
  • Mo Kα radiation
  • μ = 0.07 mm−1
  • T = 293 (2) K
  • 0.21 × 0.18 × 0.15 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: none
  • 6148 measured reflections
  • 1956 independent reflections
  • 793 reflections with I > 2σ(I)
  • R int = 0.075
  • 3 standard reflections every 100 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.072
  • wR(F 2) = 0.233
  • S = 1.02
  • 1956 reflections
  • 110 parameters
  • H-atom parameters constrained
  • Δρmax = 0.19 e Å−3
  • Δρmin = −0.14 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: NRCVAX (Gabe et al., 1989 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL/PC (Sheldrick, 1990 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807061028/hg2328sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807061028/hg2328Isup2.hkl

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

Acknowledgments

The authors thank the Natural Science Foundation of Shandong Province (grant No. Y2006B08).

supplementary crystallographic information

Comment

It is now well established that conformational characteristics of the polyaniline polymer play a crucial role for its physical properties, including transport characteristics (Boyer et al., 2000). Detailed analysis of the crystal structures of polyaniline oligomers containing alternating benzoid and quinoid rings with amine and/or imine groups can help in the understanding of the spectroscopic behaviour of the compounds and possibles mechanism for their electrical conductivity (Hadek,1968; Hadek et al., 1969). Here we report the crystal structure of the title compound, (I).

The structure of (I) consists of discrete molecules disposed about a crystallographic inversion centre with half the molecule comprising the asymmetric unit (Fig. 1). The atoms (N1, C1 - C7) are planar with the greatest deviation from planarity for N1 of 0.042 (1) Å). The bond lengths and angles are usual for this type of compound (Boyer et al., 2000). The mean planes p1(C2 - C7) and p2(C8 - C10,C8a - C10a) make a dihedral angle of 88.06 (1)°. The dihedral angle formed by ring (N1,C1 - C7)and ring (N1,C5 - C11,N1a,C5a) is 1.52 (1)°. The crystal packing (Fig.2) is stabilized by van der Waals forces.

Experimental

P-aminotoluene (2.14 g, 0.02 mol) was dissolved in water (100 ml), then sodium carbonate (0.53 g, 0.005 mol), sodium hydroxide (0.80 g, 0.02 mol) and potassium permanganate (1.58 g, 0.01 mol) was added with stirring. The mixture was allowed to react at room temperature for 12 h to give a precipitate which wasfiltered and recrystallized from acetone to afford the title compound (0.956 g, yield 89.5%). Single crystals suitable for X-ray measurements were obtained by recrystallization from acetone at room temperature.

Refinement

H atoms were fixed geometrically and allowed to ride on their parent atoms, with C—H distances of 0.93–0.96 Å and with Uiso=1.2–1.5 Ueq of the parent atoms.

Figures

Fig. 1.
The molecular structure and atom-labeling scheme for (I), with displacement ellipsoids drawn at the 30% probability level. 'A' atoms were generated by symmetry (-x + 1/3, -y + 2/3, -z - 1/3).
Fig. 2.
The crystal packing of (I),viewed down the c axis.

Crystal data

C22H22N2Z = 9
Mr = 314.42F000 = 1512
Trigonal, R3Dx = 1.155 Mg m3
Hall symbol: -R 3Mo Kα radiation λ = 0.71073 Å
a = 21.173 (8) ÅCell parameters from 25 reflections
b = 21.173 (8) Åθ = 4–14º
c = 10.476 (2) ŵ = 0.07 mm1
α = 90ºT = 293 (2) K
β = 90ºBlock, red
γ = 120º0.21 × 0.18 × 0.15 mm
V = 4067 (2) Å3

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.075
Radiation source: fine-focus sealed tubeθmax = 27.0º
Monochromator: graphiteθmin = 1.9º
T = 293(2) Kh = −26→26
ω scansk = −26→26
Absorption correction: nonel = −12→0
6148 measured reflections3 standard reflections
1956 independent reflections every 100 reflections
793 reflections with I > 2σ(I) intensity decay: none

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.072  w = 1/[σ2(Fo2) + (0.1023P)2 + 1.7438P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.233(Δ/σ)max < 0.001
S = 1.02Δρmax = 0.19 e Å3
1956 reflectionsΔρmin = −0.14 e Å3
110 parametersExtinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0029 (9)
Secondary atom site location: difference Fourier map

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
N10.17771 (14)0.28153 (14)0.0673 (3)0.0845 (9)
C1−0.0660 (2)0.1028 (3)0.3942 (4)0.1275 (17)
H1B−0.07690.13300.44740.191*
H1C−0.05290.07400.44680.191*
H1D−0.10810.07120.34410.191*
C2−0.00306 (19)0.1504 (2)0.3064 (3)0.0882 (11)
C30.0232 (2)0.1207 (2)0.2204 (5)0.1262 (16)
H3A0.00100.07020.21490.151*
C40.0822 (2)0.1636 (2)0.1401 (5)0.1197 (15)
H4A0.09880.14130.08360.144*
C50.11505 (18)0.23690 (19)0.1441 (3)0.0743 (9)
C60.0891 (2)0.2665 (2)0.2299 (4)0.1182 (15)
H6A0.11110.31700.23580.142*
C70.0306 (3)0.2232 (3)0.3089 (4)0.1189 (15)
H7A0.01410.24560.36560.143*
C80.10079 (16)0.28723 (16)−0.1018 (3)0.0740 (9)
H8A0.05790.2564−0.05830.089*
C90.16973 (16)0.30428 (16)−0.0440 (3)0.0707 (9)
C100.23710 (16)0.35227 (17)−0.1164 (3)0.0730 (9)
C110.30536 (15)0.36974 (17)−0.0619 (3)0.0810 (10)
H11A0.34390.4007−0.11920.122*
H11B0.30680.3257−0.04740.122*
H11C0.31150.39460.01780.122*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0729 (18)0.093 (2)0.092 (2)0.0442 (16)−0.0040 (15)0.0096 (17)
C10.103 (3)0.172 (4)0.109 (3)0.070 (3)0.021 (3)0.052 (3)
C20.082 (2)0.112 (3)0.081 (2)0.055 (2)−0.003 (2)0.018 (2)
C30.105 (3)0.081 (3)0.179 (4)0.036 (2)0.031 (3)0.017 (3)
C40.111 (3)0.089 (3)0.150 (4)0.043 (3)0.028 (3)−0.012 (3)
C50.071 (2)0.078 (2)0.081 (2)0.0428 (19)−0.0086 (18)0.0033 (19)
C60.139 (4)0.081 (3)0.140 (4)0.059 (3)0.036 (3)0.006 (3)
C70.142 (4)0.104 (3)0.115 (3)0.064 (3)0.043 (3)0.011 (3)
C80.0603 (19)0.075 (2)0.090 (2)0.0369 (16)0.0000 (17)0.0017 (18)
C90.070 (2)0.068 (2)0.082 (2)0.0400 (17)−0.0039 (18)−0.0034 (17)
C100.065 (2)0.074 (2)0.086 (2)0.0388 (17)−0.0052 (17)−0.0016 (17)
C110.0528 (18)0.093 (2)0.097 (2)0.0360 (17)0.0036 (17)0.0140 (19)

Geometric parameters (Å, °)

N1—C91.305 (4)C6—C71.388 (5)
N1—C51.430 (4)C6—H6A0.9300
C1—C21.516 (5)C7—H7A0.9300
C1—H1B0.9600C8—C10i1.360 (4)
C1—H1C0.9600C8—C91.449 (4)
C1—H1D0.9600C8—H8A0.9300
C2—C71.336 (5)C9—C101.481 (4)
C2—C31.365 (5)C10—C8i1.360 (4)
C3—C41.399 (6)C10—C111.420 (4)
C3—H3A0.9300C11—H11A0.9600
C4—C51.347 (5)C11—H11B0.9600
C4—H4A0.9300C11—H11C0.9600
C5—C61.359 (5)
C9—N1—C5119.9 (3)C5—C6—H6A119.2
C2—C1—H1B109.5C7—C6—H6A119.2
C2—C1—H1C109.5C2—C7—C6122.4 (4)
H1B—C1—H1C109.5C2—C7—H7A118.8
C2—C1—H1D109.5C6—C7—H7A118.8
H1B—C1—H1D109.5C10i—C8—C9122.7 (3)
H1C—C1—H1D109.5C10i—C8—H8A118.6
C7—C2—C3116.0 (4)C9—C8—H8A118.6
C7—C2—C1122.6 (4)N1—C9—C8125.6 (3)
C3—C2—C1121.3 (4)N1—C9—C10116.9 (3)
C2—C3—C4122.3 (4)C8—C9—C10117.5 (3)
C2—C3—H3A118.8C8i—C10—C11121.6 (3)
C4—C3—H3A118.8C8i—C10—C9119.8 (3)
C5—C4—C3120.6 (4)C11—C10—C9118.6 (3)
C5—C4—H4A119.7C10—C11—H11A109.5
C3—C4—H4A119.7C10—C11—H11B109.5
C4—C5—C6117.2 (4)H11A—C11—H11B109.5
C4—C5—N1121.2 (3)C10—C11—H11C109.5
C6—C5—N1121.5 (3)H11A—C11—H11C109.5
C5—C6—C7121.5 (4)H11B—C11—H11C109.5

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2328).

References

  • Boyer, I., Quillard, S., Corraze, B., Deniard, P. & Evain, M. (2000). Acta Cryst. C56, e159. [PubMed]
  • Enraf–Nonius (1989). CAD-4 Software Version 5.0. Enraf–Nonius, Delft, The Netherlands.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S. (1989). J. Appl. Cryst.22, 384–387.
  • Hadek, V. (1968). Solid State Commun.6, 337–340.
  • Hadek, V., Zach, P., Ulbert, K. & Honzl, J. (1969). Collect. Czech. Chem. Commun.34, 3139–3144.
  • Sheldrick, G. M. (1990). SHELXTL/PC Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (1997). SHELXL97 and SHELXS97 University of Göttingen, Germany.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography