organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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(Z)-3-Chloro-N-[(Z)-3-(3-chloro-2-methyl­phenyl­imino)­butan-2-yl­­idene]-2-methyl­aniline

aKey Laboratory of Eco-Environment-Related Polymer Materials of the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province, College of Chemistry & Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
*Correspondence e-mail: jianchaoyuan@nwnu.edu.cn

(Received 14 November 2011; accepted 2 December 2011; online 10 December 2011)

In the title compound, C18H18Cl2N2, the complete molecule is generated by the application of C2 symmetry. The C=N bond has an E configuration. The dihedral angle between the benzene ring and the 1,4-diaza­butadiene plane is 66.81 (9)°.

Related literature

For background to the applications of the olefin polymerization Ni(II)-α-diimine catalysts, see: Johnson et al. (1995[Johnson, L. K., Killian, C. M. & Brookhart, M. (1995). J. Am. Chem. Soc. 117, 6414-6415.]); Killian et al. (1996[Killian, C. M., Tempel, D. J., Johnson, L. K. & Brookhart, M. (1996). J. Am. Chem. Soc. 118, 11664-11665.]). For the effect of the ligand structure on the activity of the catalyst and properties of the products, see: Popeney & Guan (2010[Popeney, C. S. & Guan, Z. B. (2010). Macromolecules, 43, 4091-4097.]); Popeney et al. (2011[Popeney, C. S., Levins, C. M. & Guan, Z. B. (2011). Organometallics, 30, 2432-2452.]); Yuan et al. (2005[Yuan, J. C., SiIva, L. C., Gomes, P. T., Valerga, P., Campos, J. M., Ribeiro, M. R., Chien, J. C. W. & Marques, M. M. (2005). Polymer, 46, 2122-2132.]). For related structures, see: Kose & McKee (2011[Kose, M. & McKee, V. (2011). Acta Cryst. E67, o3193.]); Wei et al. (2011[Wei, T.-B., Lu, Y.-Y., Cao, C., Yao, H. & Zhang, Y.-M. (2011). Acta Cryst. E67, o1833.]).

[Scheme 1]

Experimental

Crystal data
  • C18H18Cl2N2

  • Mr = 333.24

  • Monoclinic, P 21 /n

  • a = 8.032 (6) Å

  • b = 7.372 (5) Å

  • c = 14.475 (10) Å

  • β = 93.533 (7)°

  • V = 855.5 (11) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 0.38 mm−1

  • T = 296 K

  • 0.23 × 0.21 × 0.19 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2008[Bruker (2008). SAINT, APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.918, Tmax = 0.932

  • 5279 measured reflections

  • 1588 independent reflections

  • 1199 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.039

  • wR(F2) = 0.115

  • S = 1.06

  • 1588 reflections

  • 102 parameters

  • H-atom parameters constrained

  • Δρmax = 0.22 e Å−3

  • Δρmin = −0.28 e Å−3

Data collection: APEX2 (Bruker, 2008[Bruker (2008). SAINT, APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2008[Bruker (2008). SAINT, APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


Comment top

There is a considerable interest in the development of new late transition metal catalysts for the polymerization of α-olefins since Brookhart discovered highly active α-diimine nickel catalysts (Johnson et al., 1995; Killian et al., 1996). It is well known that the ligand structure had significant influence on the product properties and polymerization activities (Popeney & Guan, 2010; Popeney et al., 2011; Yuan et al., 2005). In this study, we designed and synthesized the title compound as a bidentate ligand, and its molecular structure was characterized by X-ray diffraction. In the solid state, the ligand exhibits a C2 symmetry. The single bond of 1,4-diazabutadiene fragment is (E)-configured. The dihedral angle between the benzene ring and 1,4-diazabutadiene plane is 66.81 (9)°. (Figure 1.) In the crystal packing, there is no hydrogen-bond between the ligand molecules.

Related literature top

For background to the applications of the olefin polymerization Ni(II)-α-diimine catalysts, see: Johnson et al. (1995); Killian et al. (1996). For the effect of the ligand structure on the activity of the catalyst and properties of the products, see: Popeney & Guan (2010); Popeney et al. (2011); Yuan et al. (2005). For related structures, see: Kose & McKee (2011); Wei et al. (2011).

Experimental top

Formic acid (0.5 ml) was added to a stirred solution of 2,3-butanedione (0.052 g, 0.6 mmol) and 3-chloro-2-methylaniline (0.0.170 g, 1.2 mmol) in methanol (20 ml). The mixture was refluxed for 24 h, then cooled and the precipitate was separated by filtration. The solid was recrystallized from dichloromethane/cyclohexane (v/v = 8:1), washed with cold ethanol and dried under vacuum to give the title ligand 0.18 g (90%). Anal. Calcd. for C18H18Cl2N2: C, 64.87; H, 5.44; N,8.41; Cl, 21.28. Found: C, 64.97; H, 5.33; N, 8.21; Cl, 21.59. Crystals suitable for X-ray structure determination were grown from a solution of the title compound in a mixture of cyclohexane/dichloromethane (1:2, v/v).

Refinement top

All hydrogen atoms were placed in calculated positions with C—H distances of 0.93 and 0.96 Å for aryl and methyl type H-atoms. They were included in the refinement in a riding model approximation, respectively. The H-atoms were assigned Uiso = 1.2 times Ueq of the aryl C atoms and 1.5 times Ueq of the methyl C atoms.

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
[Figure 1] Fig. 1. Molecular structure of the title compound, using 30% probability level ellipsoids. Primed atoms are related by the symmetry code (-x + 1, -y + 1, -z).
(Z)-3-Chloro-N-[(Z)-3-(3-chloro-2-methylphenylimino)butan- 2-ylidene]-2-methylaniline top
Crystal data top
C18H18Cl2N2F(000) = 348
Mr = 333.24Dx = 1.294 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2237 reflections
a = 8.032 (6) Åθ = 2.8–28.0°
b = 7.372 (5) ŵ = 0.38 mm1
c = 14.475 (10) ÅT = 296 K
β = 93.533 (7)°Block, colorless
V = 855.5 (11) Å30.23 × 0.21 × 0.19 mm
Z = 2
Data collection top
Bruker APEXII CCD
diffractometer
1588 independent reflections
Radiation source: fine-focus sealed tube1199 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.5°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
h = 99
Tmin = 0.918, Tmax = 0.932k = 88
5279 measured reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.115H-atom parameters constrained
S = 1.06 w = 1/[σ2(Fo2) + (0.0428P)2 + 0.4563P]
where P = (Fo2 + 2Fc2)/3
1588 reflections(Δ/σ)max = 0.001
102 parametersΔρmax = 0.22 e Å3
0 restraintsΔρmin = 0.28 e Å3
Crystal data top
C18H18Cl2N2V = 855.5 (11) Å3
Mr = 333.24Z = 2
Monoclinic, P21/nMo Kα radiation
a = 8.032 (6) ŵ = 0.38 mm1
b = 7.372 (5) ÅT = 296 K
c = 14.475 (10) Å0.23 × 0.21 × 0.19 mm
β = 93.533 (7)°
Data collection top
Bruker APEXII CCD
diffractometer
1588 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)
1199 reflections with I > 2σ(I)
Tmin = 0.918, Tmax = 0.932Rint = 0.034
5279 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.115H-atom parameters constrained
S = 1.06Δρmax = 0.22 e Å3
1588 reflectionsΔρmin = 0.28 e Å3
102 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
xyzUiso*/Ueq
C10.4602 (2)0.2982 (3)0.17826 (13)0.0373 (5)
C20.5314 (2)0.3432 (3)0.26633 (13)0.0382 (5)
C30.5281 (3)0.2084 (3)0.33347 (14)0.0451 (5)
C40.4584 (3)0.0403 (3)0.31793 (16)0.0532 (6)
H40.45890.04530.36510.064*
C50.3875 (3)0.0005 (3)0.23100 (16)0.0532 (6)
H50.33910.11240.21920.064*
C60.3887 (3)0.1286 (3)0.16168 (15)0.0469 (5)
H60.34110.10130.10310.056*
C70.6047 (3)0.5274 (3)0.28511 (17)0.0603 (7)
H7A0.56400.57480.34120.090*
H7B0.57300.60700.23460.090*
H7C0.72410.51820.29160.090*
C80.5174 (2)0.4244 (3)0.03386 (13)0.0383 (5)
C90.6332 (4)0.2775 (3)0.00740 (18)0.0672 (8)
H9A0.66050.20170.06010.101*
H9B0.73340.33040.01360.101*
H9C0.58030.20580.04140.101*
Cl10.61699 (10)0.25335 (11)0.44457 (4)0.0788 (3)
N10.4462 (2)0.4357 (2)0.10980 (11)0.0421 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0400 (11)0.0413 (12)0.0309 (10)0.0048 (9)0.0052 (8)0.0042 (8)
C20.0360 (10)0.0453 (12)0.0334 (11)0.0021 (9)0.0046 (8)0.0013 (9)
C30.0424 (12)0.0634 (15)0.0295 (11)0.0035 (10)0.0009 (8)0.0075 (10)
C40.0594 (14)0.0556 (15)0.0455 (13)0.0024 (12)0.0089 (11)0.0188 (11)
C50.0584 (14)0.0491 (14)0.0527 (14)0.0101 (11)0.0075 (11)0.0077 (11)
C60.0527 (13)0.0505 (14)0.0370 (12)0.0034 (10)0.0001 (9)0.0003 (10)
C70.0726 (17)0.0586 (16)0.0487 (14)0.0108 (13)0.0031 (12)0.0026 (12)
C80.0443 (11)0.0404 (11)0.0299 (10)0.0026 (9)0.0003 (8)0.0024 (9)
C90.0875 (19)0.0616 (16)0.0553 (15)0.0312 (14)0.0260 (14)0.0189 (13)
Cl10.0917 (6)0.1055 (6)0.0367 (4)0.0069 (4)0.0154 (3)0.0111 (3)
N10.0523 (11)0.0433 (10)0.0308 (9)0.0050 (8)0.0021 (7)0.0058 (8)
Geometric parameters (Å, º) top
C1—C61.391 (3)C6—H60.9300
C1—C21.404 (3)C7—H7A0.9600
C1—N11.417 (3)C7—H7B0.9600
C2—C31.392 (3)C7—H7C0.9600
C2—C71.498 (3)C8—N11.273 (3)
C3—C41.373 (3)C8—C91.493 (3)
C3—Cl11.751 (2)C8—C8i1.500 (4)
C4—C51.380 (3)C9—H9A0.9600
C4—H40.9300C9—H9B0.9600
C5—C61.378 (3)C9—H9C0.9600
C5—H50.9300
C6—C1—C2120.64 (19)C1—C6—H6119.6
C6—C1—N1120.53 (18)C2—C7—H7A109.5
C2—C1—N1118.46 (19)C2—C7—H7B109.5
C3—C2—C1116.2 (2)H7A—C7—H7B109.5
C3—C2—C7123.0 (2)C2—C7—H7C109.5
C1—C2—C7120.82 (19)H7A—C7—H7C109.5
C4—C3—C2123.8 (2)H7B—C7—H7C109.5
C4—C3—Cl1117.42 (17)N1—C8—C9126.12 (19)
C2—C3—Cl1118.82 (18)N1—C8—C8i116.1 (2)
C3—C4—C5118.8 (2)C9—C8—C8i117.8 (2)
C3—C4—H4120.6C8—C9—H9A109.5
C5—C4—H4120.6C8—C9—H9B109.5
C6—C5—C4119.8 (2)H9A—C9—H9B109.5
C6—C5—H5120.1C8—C9—H9C109.5
C4—C5—H5120.1H9A—C9—H9C109.5
C5—C6—C1120.8 (2)H9B—C9—H9C109.5
C5—C6—H6119.6C8—N1—C1122.45 (18)
C6—C1—C2—C31.1 (3)Cl1—C3—C4—C5179.88 (18)
N1—C1—C2—C3174.16 (17)C3—C4—C5—C60.4 (3)
C6—C1—C2—C7178.5 (2)C4—C5—C6—C10.2 (3)
N1—C1—C2—C75.4 (3)C2—C1—C6—C50.6 (3)
C1—C2—C3—C40.9 (3)N1—C1—C6—C5173.5 (2)
C7—C2—C3—C4178.6 (2)C9—C8—N1—C14.5 (3)
C1—C2—C3—Cl1179.13 (14)C8i—C8—N1—C1176.6 (2)
C7—C2—C3—Cl11.3 (3)C6—C1—N1—C867.6 (3)
C2—C3—C4—C50.2 (4)C2—C1—N1—C8119.4 (2)
Symmetry code: (i) x+1, y+1, z.

Experimental details

Crystal data
Chemical formulaC18H18Cl2N2
Mr333.24
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)8.032 (6), 7.372 (5), 14.475 (10)
β (°) 93.533 (7)
V3)855.5 (11)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.23 × 0.21 × 0.19
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2008)
Tmin, Tmax0.918, 0.932
No. of measured, independent and
observed [I > 2σ(I)] reflections
5279, 1588, 1199
Rint0.034
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.115, 1.06
No. of reflections1588
No. of parameters102
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.28

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

 

Acknowledgements

We thank the National Natural Science Foundation of China (20964003) for funding. We also thank the Key Laboratory of Eco Environment-Related Polymer Materials of Ministry of Education, Key Laboratory of Polymer Mat­erials of Gansu Province (Northwest Normal University), for financial support

References

First citationBruker (2008). SAINT, APEX2 and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationJohnson, L. K., Killian, C. M. & Brookhart, M. (1995). J. Am. Chem. Soc. 117, 6414–6415.  CrossRef CAS Web of Science
First citationKillian, C. M., Tempel, D. J., Johnson, L. K. & Brookhart, M. (1996). J. Am. Chem. Soc. 118, 11664–11665.  CrossRef CAS Web of Science
First citationKose, M. & McKee, V. (2011). Acta Cryst. E67, o3193.  Web of Science CSD CrossRef IUCr Journals
First citationPopeney, C. S. & Guan, Z. B. (2010). Macromolecules, 43, 4091–4097.  Web of Science CrossRef CAS
First citationPopeney, C. S., Levins, C. M. & Guan, Z. B. (2011). Organometallics, 30, 2432–2452.  Web of Science CrossRef CAS
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals
First citationWei, T.-B., Lu, Y.-Y., Cao, C., Yao, H. & Zhang, Y.-M. (2011). Acta Cryst. E67, o1833.  Web of Science CSD CrossRef IUCr Journals
First citationYuan, J. C., SiIva, L. C., Gomes, P. T., Valerga, P., Campos, J. M., Ribeiro, M. R., Chien, J. C. W. & Marques, M. M. (2005). Polymer, 46, 2122–2132.  Web of Science CSD CrossRef CAS

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