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

Jian, F.-F.; Zhuang, R.-R.; Wang, K.-F.; Wang, J.

doi:10.1107/S1600536807061028

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o78

https://doi.org/10.1107/S1600536807061028

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

Fang-Fang Jian,^a ^* Rui-Rui Zhuang,^a Ke-Fei Wang ^a and Jing Wang ^a

^aNew Materials and Function Coordination Chemistry Laboratory, Qingdao University of Science and Technology, Qingdao 266042, People's Republic of China
^*Correspondence e-mail: ffj2003@163169.net

(Received 25 October 2007; accepted 20 November 2007; online 6 December 2007)

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 ); Hadek (1968 ); Hadek et al. (1969 )

Experimental

Crystal data

C₂₂H₂₂N₂
M_r = 314.42
Trigonal, $[R \overline 3]$
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[F² > 2σ(F²)] = 0.072
wR(F²) = 0.233
S = 1.02
1956 reflections
110 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807061028/hg2328Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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

Computing details top

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

Figures top

	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.

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

Crystal data top

C₂₂H₂₂N₂	D_x = 1.155 Mg m⁻³
M_r = 314.42	Mo Kα radiation, λ = 0.71073 Å
Trigonal, R3	Cell parameters from 25 reflections
Hall symbol: -R 3	θ = 4–14°
a = 21.173 (8) Å	µ = 0.07 mm⁻¹
c = 10.476 (2) Å	T = 293 K
V = 4067 (2) Å³	Block, red
Z = 9	0.21 × 0.18 × 0.15 mm
F(000) = 1512

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.075
Radiation source: fine-focus sealed tube	θ_max = 27.0°, θ_min = 1.9°
Graphite monochromator	h = −26→26
ω scans	k = −26→26
6148 measured reflections	l = −12→0
1956 independent reflections	3 standard reflections every 100 reflections
793 reflections with I > 2σ(I)	intensity decay: none

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.072	H-atom parameters constrained
wR(F²) = 0.233	w = 1/[σ²(F_o²) + (0.1023P)² + 1.7438P] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max < 0.001
1956 reflections	Δρ_max = 0.19 e Å⁻³
110 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXL, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0029 (9)

Crystal data top

C₂₂H₂₂N₂	Z = 9
M_r = 314.42	Mo Kα radiation
Trigonal, R3	µ = 0.07 mm⁻¹
a = 21.173 (8) Å	T = 293 K
c = 10.476 (2) Å	0.21 × 0.18 × 0.15 mm
V = 4067 (2) Å³

Data collection top

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

Refinement top

R[F² > 2σ(F²)] = 0.072	0 restraints
wR(F²) = 0.233	H-atom parameters constrained
S = 1.02	Δρ_max = 0.19 e Å⁻³
1956 reflections	Δρ_min = −0.14 e Å⁻³
110 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
N1	0.17771 (14)	0.28153 (14)	0.0673 (3)	0.0845 (9)
C1	−0.0660 (2)	0.1028 (3)	0.3942 (4)	0.1275 (17)
H1B	−0.0769	0.1330	0.4474	0.191*
H1C	−0.0529	0.0740	0.4468	0.191*
H1D	−0.1081	0.0712	0.3441	0.191*
C2	−0.00306 (19)	0.1504 (2)	0.3064 (3)	0.0882 (11)
C3	0.0232 (2)	0.1207 (2)	0.2204 (5)	0.1262 (16)
H3A	0.0010	0.0702	0.2149	0.151*
C4	0.0822 (2)	0.1636 (2)	0.1401 (5)	0.1197 (15)
H4A	0.0988	0.1413	0.0836	0.144*
C5	0.11505 (18)	0.23690 (19)	0.1441 (3)	0.0743 (9)
C6	0.0891 (2)	0.2665 (2)	0.2299 (4)	0.1182 (15)
H6A	0.1111	0.3170	0.2358	0.142*
C7	0.0306 (3)	0.2232 (3)	0.3089 (4)	0.1189 (15)
H7A	0.0141	0.2456	0.3656	0.143*
C8	0.10079 (16)	0.28723 (16)	−0.1018 (3)	0.0740 (9)
H8A	0.0579	0.2564	−0.0583	0.089*
C9	0.16973 (16)	0.30428 (16)	−0.0440 (3)	0.0707 (9)
C10	0.23710 (16)	0.35227 (17)	−0.1164 (3)	0.0730 (9)
C11	0.30536 (15)	0.36974 (17)	−0.0619 (3)	0.0810 (10)
H11A	0.3439	0.4007	−0.1192	0.122*
H11B	0.3068	0.3257	−0.0474	0.122*
H11C	0.3115	0.3946	0.0178	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0729 (18)	0.093 (2)	0.092 (2)	0.0442 (16)	−0.0040 (15)	0.0096 (17)
C1	0.103 (3)	0.172 (4)	0.109 (3)	0.070 (3)	0.021 (3)	0.052 (3)
C2	0.082 (2)	0.112 (3)	0.081 (2)	0.055 (2)	−0.003 (2)	0.018 (2)
C3	0.105 (3)	0.081 (3)	0.179 (4)	0.036 (2)	0.031 (3)	0.017 (3)
C4	0.111 (3)	0.089 (3)	0.150 (4)	0.043 (3)	0.028 (3)	−0.012 (3)
C5	0.071 (2)	0.078 (2)	0.081 (2)	0.0428 (19)	−0.0086 (18)	0.0033 (19)
C6	0.139 (4)	0.081 (3)	0.140 (4)	0.059 (3)	0.036 (3)	0.006 (3)
C7	0.142 (4)	0.104 (3)	0.115 (3)	0.064 (3)	0.043 (3)	0.011 (3)
C8	0.0603 (19)	0.075 (2)	0.090 (2)	0.0369 (16)	0.0000 (17)	0.0017 (18)
C9	0.070 (2)	0.068 (2)	0.082 (2)	0.0400 (17)	−0.0039 (18)	−0.0034 (17)
C10	0.065 (2)	0.074 (2)	0.086 (2)	0.0388 (17)	−0.0052 (17)	−0.0016 (17)
C11	0.0528 (18)	0.093 (2)	0.097 (2)	0.0360 (17)	0.0036 (17)	0.0140 (19)

Geometric parameters (Å, º) top

N1—C9	1.305 (4)	C6—C7	1.388 (5)
N1—C5	1.430 (4)	C6—H6A	0.9300
C1—C2	1.516 (5)	C7—H7A	0.9300
C1—H1B	0.9600	C8—C10ⁱ	1.360 (4)
C1—H1C	0.9600	C8—C9	1.449 (4)
C1—H1D	0.9600	C8—H8A	0.9300
C2—C7	1.336 (5)	C9—C10	1.481 (4)
C2—C3	1.365 (5)	C10—C8ⁱ	1.360 (4)
C3—C4	1.399 (6)	C10—C11	1.420 (4)
C3—H3A	0.9300	C11—H11A	0.9600
C4—C5	1.347 (5)	C11—H11B	0.9600
C4—H4A	0.9300	C11—H11C	0.9600
C5—C6	1.359 (5)

C9—N1—C5	119.9 (3)	C5—C6—H6A	119.2
C2—C1—H1B	109.5	C7—C6—H6A	119.2
C2—C1—H1C	109.5	C2—C7—C6	122.4 (4)
H1B—C1—H1C	109.5	C2—C7—H7A	118.8
C2—C1—H1D	109.5	C6—C7—H7A	118.8
H1B—C1—H1D	109.5	C10ⁱ—C8—C9	122.7 (3)
H1C—C1—H1D	109.5	C10ⁱ—C8—H8A	118.6
C7—C2—C3	116.0 (4)	C9—C8—H8A	118.6
C7—C2—C1	122.6 (4)	N1—C9—C8	125.6 (3)
C3—C2—C1	121.3 (4)	N1—C9—C10	116.9 (3)
C2—C3—C4	122.3 (4)	C8—C9—C10	117.5 (3)
C2—C3—H3A	118.8	C8ⁱ—C10—C11	121.6 (3)
C4—C3—H3A	118.8	C8ⁱ—C10—C9	119.8 (3)
C5—C4—C3	120.6 (4)	C11—C10—C9	118.6 (3)
C5—C4—H4A	119.7	C10—C11—H11A	109.5
C3—C4—H4A	119.7	C10—C11—H11B	109.5
C4—C5—C6	117.2 (4)	H11A—C11—H11B	109.5
C4—C5—N1	121.2 (3)	C10—C11—H11C	109.5
C6—C5—N1	121.5 (3)	H11A—C11—H11C	109.5
C5—C6—C7	121.5 (4)	H11B—C11—H11C	109.5

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

Experimental details

Crystal data
Chemical formula	C₂₂H₂₂N₂
M_r	314.42
Crystal system, space group	Trigonal, R3
Temperature (K)	293
a, c (Å)	21.173 (8), 10.476 (2)
V (Å³)	4067 (2)
Z	9
Radiation type	Mo Kα
µ (mm⁻¹)	0.07
Crystal size (mm)	0.21 × 0.18 × 0.15

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6148, 1956, 793
R_int	0.075
(sin θ/λ)_max (Å⁻¹)	0.638

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.072, 0.233, 1.02
No. of reflections	1956
No. of parameters	110
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), NRCVAX (Gabe et al., 1989), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL/PC (Sheldrick, 1990), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

N1—C9

1.305 (4)

N1—C5

1.430 (4)

Acknowledgements

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

References

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