(Z)-N-[(Z)-3-(2,5-Di­methyl­phenyl­imino)­butan-2-yl­idene]-2,5-di­methyl­aniline

Lv, W.-X.; Li, J.; Hu, Y.-L.; Su, Y.-P.; Huang, D.-F.

doi:10.1107/S1600536814001020

organic compounds

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ISSN: 2056-9890

Volume 70| Part 2| February 2014| Page o175

doi:10.1107/S1600536814001020

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(Z)-N-[(Z)-3-(2,5-Dimethylphenylimino)butan-2-ylidene]-2,5-dimethylaniline

Wen-Xian Lv,^a Jian Li,^a Yu-Lai Hu,^a ^* Ying-Peng Su ^a and Dan-Feng Huang ^a

^aCollege of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, Gansu Province 730070, People's Republic of China
^*Correspondence e-mail: huylai@163.com

(Received 23 December 2013; accepted 15 January 2014; online 22 January 2014)

The asymmetric unit of the title compound, C₂₀H₂₄N₂, contains one half-molecule, with the single C—C bond of the 1,4-diazabutadiene fragment situated on a centre of symmetry. The benzene rings are inclined to the 1,4-diazabutadiene mean plane by 59.5 (1)°.

CCDC reference: 981625

Related literature

For the crystal structures of related compounds, see: Kuhn et al. (2001 ); Schaub & Radius (2006 ); Yuan et al. (2012 ).

Experimental

Crystal data

C₂₀H₂₄N₂
M_r = 292.42
Monoclinic, P 2₁ /n
a = 7.128 (3) Å
b = 8.304 (4) Å
c = 15.162 (7) Å
β = 96.528 (5)°
V = 891.7 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.06 mm⁻¹
T = 296 K
0.23 × 0.21 × 0.19 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ) T_min = 0.986, T_max = 0.988
4080 measured reflections
1643 independent reflections
1114 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.175
S = 1.07
1643 reflections
103 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 981625

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536814001020/cv5439sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814001020/cv5439Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814001020/cv5439Isup3.cml

checkCIF report

Comment top

In a continuation of our crystallographic study of the compounds used as α-diimine ligands for Ni^II-α-diimine olefin polymerization catalysts (Yuan et al., 2012), we present here the crystal structure of the title compound (I).

The asymmetric unit of (I) contains one half-molecule with the single C—C bond in 1,4-diazabutadiene fragment situated on a centre of symmetry (Fig. 1). The single bond of 1,4-diazabutadiene fragment is (E)-configured. The dihedral angle between the benzene ring and the 1,4-diazabutadiene plane is 59.5 (1). All bond lengths and angles in (I) are normal and correspond well to those observed in the related compounds 2,3-bis(2,6-dimethylphenyl)iminobutane (Kuhn et al., 2001), N,N'-dimesitylbutane-2,3-diimine (Schaub & Radius, 2006) and (Z)-N-[(Z)-3-(2,4-dimethylphenylimino)-butan-2- ylidene]-2,4-dimethylaniline (Yuan et al., 2012).

Related literature top

For the crystal structures of related compounds, see: Kuhn et al. (2001); Schaub & Radius (2006); Yuan et al. (2012).

Experimental top

Formic acid (1 ml) was added to a stirred solution of 2,3-butanedione (0.052 g, 0.6 mmol) and 2,5-dimethylaniline (0.145 g, 1.2 mmol) in methanol (30 ml). The mixture was refluxed for 24 h, and then the solvent was removed. The residue was purified by chromatography on silica gel with petroleum ether/ethyl ester (v/v = 20:1). The crude product was recrystallized from ethanol/dichloromethane (v/v = 8:1). The pure product was washed and dried in vacuo to give a fine yellow powder. Yield: 0.143 g (82%). Crystals suitable for X-ray structure determination were grown from a solution of the title compound in a mixture of cyclohexane/dichloromethane (v/v = 1:2).

Structure description top

For the crystal structures of related compounds, see: Kuhn et al. (2001); Schaub & Radius (2006); Yuan et al. (2012).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I), showing the atomic numbering and 30% probability displacement ellipsoids [symmetry code: (a) 2 - x, 1 - y, 1 - z].

(Z)-N-[(Z)-3-(2,5-Dimethylphenylimino)butan-2-ylidene]-2,5-dimethylaniline top

Crystal data top

C₂₀H₂₄N₂	F(000) = 316
M_r = 292.42	D_x = 1.089 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.128 (3) Å	Cell parameters from 1181 reflections
b = 8.304 (4) Å	θ = 2.7–25.0°
c = 15.162 (7) Å	µ = 0.06 mm⁻¹
β = 96.528 (5)°	T = 296 K
V = 891.7 (7) Å³	Block, yellow
Z = 2	0.23 × 0.21 × 0.19 mm

Data collection top

Bruker APEXII CCD area-detector diffractometer	1643 independent reflections
Radiation source: fine-focus sealed tube	1114 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
φ and ω scans	θ_max = 25.5°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
T_min = 0.986, T_max = 0.988	k = −9→10
4080 measured reflections	l = −12→18

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.175	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.1P)²] where P = (F_o² + 2F_c²)/3
1643 reflections	(Δ/σ)_max < 0.001
103 parameters	Δρ_max = 0.17 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₂₀H₂₄N₂	V = 891.7 (7) Å³
M_r = 292.42	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.128 (3) Å	µ = 0.06 mm⁻¹
b = 8.304 (4) Å	T = 296 K
c = 15.162 (7) Å	0.23 × 0.21 × 0.19 mm
β = 96.528 (5)°

Data collection top

Bruker APEXII CCD area-detector diffractometer	1643 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2008)	1114 reflections with I > 2σ(I)
T_min = 0.986, T_max = 0.988	R_int = 0.040
4080 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.175	H-atom parameters constrained
S = 1.07	Δρ_max = 0.17 e Å⁻³
1643 reflections	Δρ_min = −0.17 e Å⁻³
103 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
C1	1.0081 (3)	0.6052 (2)	0.30932 (11)	0.0418 (5)
C2	1.1376 (3)	0.7091 (3)	0.27639 (12)	0.0507 (6)
C3	1.0926 (3)	0.7661 (3)	0.19027 (13)	0.0604 (6)
H3	1.1760	0.8356	0.1665	0.072*
C4	0.9291 (3)	0.7230 (3)	0.13947 (13)	0.0598 (6)
H4	0.9043	0.7635	0.0821	0.072*
C5	0.7995 (3)	0.6200 (2)	0.17187 (13)	0.0513 (6)
C6	0.8429 (3)	0.5612 (2)	0.25790 (12)	0.0470 (5)
H6	0.7594	0.4912	0.2812	0.056*
C7	1.3169 (3)	0.7566 (4)	0.33116 (16)	0.0798 (8)
H7A	1.2882	0.8234	0.3795	0.120*
H7B	1.3955	0.8152	0.2949	0.120*
H7C	1.3822	0.6618	0.3542	0.120*
C8	0.6167 (4)	0.5763 (3)	0.11792 (16)	0.0819 (8)
H8A	0.5215	0.6532	0.1287	0.123*
H8B	0.5782	0.4708	0.1346	0.123*
H8C	0.6337	0.5768	0.0560	0.123*
C9	0.9622 (2)	0.5443 (2)	0.45830 (11)	0.0393 (5)
C10	0.7828 (3)	0.6367 (2)	0.45927 (12)	0.0508 (6)
H10A	0.7584	0.6973	0.4053	0.076*
H10B	0.7942	0.7090	0.5090	0.076*
H10C	0.6805	0.5633	0.4642	0.076*
N1	1.0615 (2)	0.53296 (18)	0.39391 (9)	0.0443 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0482 (11)	0.0458 (11)	0.0342 (10)	0.0095 (8)	0.0166 (8)	0.0053 (8)
C2	0.0488 (12)	0.0590 (13)	0.0469 (12)	0.0012 (9)	0.0173 (9)	0.0091 (9)
C3	0.0707 (15)	0.0649 (14)	0.0501 (12)	−0.0011 (11)	0.0271 (11)	0.0180 (10)
C4	0.0818 (16)	0.0625 (14)	0.0369 (11)	0.0159 (12)	0.0150 (11)	0.0128 (10)
C5	0.0641 (13)	0.0483 (12)	0.0415 (11)	0.0107 (9)	0.0065 (10)	0.0004 (9)
C6	0.0523 (11)	0.0492 (11)	0.0411 (11)	0.0016 (9)	0.0117 (9)	0.0056 (9)
C7	0.0618 (15)	0.102 (2)	0.0764 (16)	−0.0188 (13)	0.0104 (13)	0.0217 (14)
C8	0.0931 (19)	0.0822 (17)	0.0637 (15)	0.0037 (14)	−0.0204 (14)	0.0008 (13)
C9	0.0386 (10)	0.0450 (11)	0.0355 (9)	−0.0032 (8)	0.0088 (8)	0.0028 (8)
C10	0.0510 (12)	0.0630 (13)	0.0396 (11)	0.0125 (9)	0.0101 (9)	0.0047 (9)
N1	0.0463 (10)	0.0532 (10)	0.0353 (9)	0.0037 (7)	0.0137 (7)	0.0083 (7)

Geometric parameters (Å, º) top

C1—C6	1.386 (3)	C7—H7A	0.9600
C1—C2	1.396 (3)	C7—H7B	0.9600
C1—N1	1.428 (2)	C7—H7C	0.9600
C2—C3	1.392 (3)	C8—H8A	0.9600
C2—C7	1.496 (3)	C8—H8B	0.9600
C3—C4	1.369 (3)	C8—H8C	0.9600
C3—H3	0.9300	C9—N1	1.273 (2)
C4—C5	1.389 (3)	C9—C10	1.493 (3)
C4—H4	0.9300	C9—C9ⁱ	1.508 (3)
C5—C6	1.394 (3)	C10—H10A	0.9600
C5—C8	1.502 (3)	C10—H10B	0.9600
C6—H6	0.9300	C10—H10C	0.9600

C6—C1—C2	121.04 (16)	H7A—C7—H7B	109.5
C6—C1—N1	121.17 (17)	C2—C7—H7C	109.5
C2—C1—N1	117.46 (16)	H7A—C7—H7C	109.5
C3—C2—C1	117.04 (18)	H7B—C7—H7C	109.5
C3—C2—C7	121.47 (19)	C5—C8—H8A	109.5
C1—C2—C7	121.49 (18)	C5—C8—H8B	109.5
C4—C3—C2	121.9 (2)	H8A—C8—H8B	109.5
C4—C3—H3	119.0	C5—C8—H8C	109.5
C2—C3—H3	119.0	H8A—C8—H8C	109.5
C3—C4—C5	121.32 (18)	H8B—C8—H8C	109.5
C3—C4—H4	119.3	N1—C9—C10	126.66 (16)
C5—C4—H4	119.3	N1—C9—C9ⁱ	115.49 (19)
C4—C5—C6	117.43 (19)	C10—C9—C9ⁱ	117.84 (19)
C4—C5—C8	121.79 (19)	C9—C10—H10A	109.5
C6—C5—C8	120.8 (2)	C9—C10—H10B	109.5
C1—C6—C5	121.21 (19)	H10A—C10—H10B	109.5
C1—C6—H6	119.4	C9—C10—H10C	109.5
C5—C6—H6	119.4	H10A—C10—H10C	109.5
C2—C7—H7A	109.5	H10B—C10—H10C	109.5
C2—C7—H7B	109.5	C9—N1—C1	122.91 (15)

C6—C1—C2—C3	0.2 (3)	C2—C1—C6—C5	−0.5 (3)
N1—C1—C2—C3	173.73 (16)	N1—C1—C6—C5	−173.76 (16)
C6—C1—C2—C7	−179.7 (2)	C4—C5—C6—C1	0.6 (3)
N1—C1—C2—C7	−6.1 (3)	C8—C5—C6—C1	−177.77 (18)
C1—C2—C3—C4	−0.1 (3)	C10—C9—N1—C1	−2.7 (3)
C7—C2—C3—C4	179.8 (2)	C9ⁱ—C9—N1—C1	178.12 (18)
C2—C3—C4—C5	0.2 (3)	C6—C1—N1—C9	−61.6 (2)
C3—C4—C5—C6	−0.4 (3)	C2—C1—N1—C9	124.9 (2)
C3—C4—C5—C8	177.9 (2)

Symmetry code: (i) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₂₄N₂
M_r	292.42
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.128 (3), 8.304 (4), 15.162 (7)
β (°)	96.528 (5)
V (Å³)	891.7 (7)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.06
Crystal size (mm)	0.23 × 0.21 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2008)
T_min, T_max	0.986, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	4080, 1643, 1114
R_int	0.040

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.175, 1.07
No. of reflections	1643
No. of parameters	103
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.17, −0.17

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The authors are grateful for financial support from the National Natural Science Foundation of China (grant No. 21062016), the Key Laboratory of Polymer Materials of Gansu Province (Northwest Normal University), the Bioactive Product Engineering Research Centre for Gansu Distinctive Plants and the State Key Laboratory of Applied Organic Chemistry, Lanzhou University.

References

Bruker (2008). SADABS, SAINT and APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Kuhn, N., Steimann, M. & Walker, I. (2001). Z. Kristallogr. New Cryst. Struct. 216, 318–319. CAS Google Scholar
Schaub, T. & Radius, U. (2006). Z. Anorg. Allg. Chem. 632, 807–813. Web of Science CSD CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yuan, J., Miao, C., Xu, W. & Yuan, B. (2012). Acta Cryst. E68, o164. Web of Science CSD CrossRef IUCr Journals Google Scholar

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