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

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ISSN: 2056-9890

(E)-N-{(E)-2-[(3,5-Di­methylbi­phenyl-4-yl)imino]­acenaphthen-1-yl­­idene}-2,6-di­methyl-4-phenyl­aniline

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 15 December 2011; online 21 December 2011)

The title compound, C40H32N2, has crystallographic twofold rotation symmetry, with two C atoms lying on the axis. The dihedral angle between the two benzene rings of the 4-phenyl-2,6-dimethyl­phenyl group is 35.74 (17)°. The acenaphthene ring makes an angle of 76.93 (11)° with the benzene ring bonded to the N atom and an angle of 41.53 (13)° with the other benzene ring.

Related literature

The title compound was synthesized as an α-diimine ligand for use in NiIIα-diimine olefin polymerization catalysts. For applications of metal-organic polymerization 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.]); Popeney et al. (2005[Popeney, C. & Guan, Z. B. (2005). Organometallics, 24, 1145-1155.], 2010[Popeney, C. S. & Guan, Z. B. (2010). Macromolecules, 43, 4091-4097.], 2011[Popeney, C. S., Levins, C. M. & Guan, Z. B. (2011). Organometallics, 30, 2432-2452.]). For a related structure, see: Lohr et al. (2011[Lohr, T. L., Piers, W. E. & Parvez, M. (2011). Acta Cryst. E67, o2280.]).

[Scheme 1]

Experimental

Crystal data
  • C40H32N2

  • Mr = 540.68

  • Monoclinic, C 2/c

  • a = 22.994 (14) Å

  • b = 8.676 (5) Å

  • c = 18.652 (18) Å

  • β = 124.084 (4)°

  • V = 3082 (4) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.07 mm−1

  • T = 296 K

  • 0.23 × 0.21 × 0.19 mm

Data collection
  • Bruker APEXII CCD diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2008a[Sheldrick, G. M. (2008a). SADABS. University of Göttingen, Germany.]) Tmin = 0.985, Tmax = 0.987

  • 10667 measured reflections

  • 2857 independent reflections

  • 1596 reflections with I > 2σ(I)

  • Rint = 0.031

Refinement
  • R[F2 > 2σ(F2)] = 0.059

  • wR(F2) = 0.211

  • S = 1.16

  • 2857 reflections

  • 193 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.20 e Å−3

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

Supporting information


Comment top

In recent years, α-diimine nickel catalysts have drawn wide-spread attention due to their high catalytic activity in ethylene polymerization (Johnson et al., 1995; Killian et al., 1996). It is well known that the ligand structure has significant influence on the product properties and polymerization activities (Popeney et al., 2011; Popeney et al., 2010; Popeney 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.

Related literature top

The title compound was synthesized as an α-diimine ligand for use in NiIIα-diimine olefin polymerization catalysts. For applications of metal-organic polymerization catalysts, see: Johnson et al. (1995); Killian et al. (1996); Popeney et al. (2005, 2010, 2011). For a related structure, see: Lohr et al. (2011).

Experimental top

Formic acid (1 ml) was added to a stirred solution of acenaphthenequinone (0.25 g, 1.37 mmol) and 4-phenyl-2,6-dimehylaniline (0.54 g, 2.74 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 ethanol/dichloromethane (v/v = 8:1), washed and dried under vacuum. Yield: 0.55 g (74%). Anal. Calcd. for C40H32N2: C, 88.85; H, 5.97; N, 5.18. Found: C, 88.91; H, 6.03; N, 5.06. 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) by slow evaporation.

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, respectively. They were included in the refinement in a riding model approximation. 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, 2008b); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008b); molecular graphics: SHELXTL (Sheldrick, 2008b); software used to prepare material for publication: SHELXTL (Sheldrick, 2008b).

Figures top
[Figure 1] Fig. 1. Structure of the title compound, with displacement ellipsoids drawn at the 30% probability level. H-atoms have been excluded for clarity. The atom name suffix indicates symmetry code (a): –x, y, –z + 1/2.
(E)-N-{(E)-2-[(3,5-Dimethylbiphenyl-4- yl)imino]acenaphthen-1-ylidene}-2,6-dimethyl-4-phenylaniline top
Crystal data top
C40H32N2F(000) = 1144
Mr = 540.68Dx = 1.165 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
a = 22.994 (14) ÅCell parameters from 3073 reflections
b = 8.676 (5) Åθ = 2.1–25.7°
c = 18.652 (18) ŵ = 0.07 mm1
β = 124.084 (4)°T = 296 K
V = 3082 (4) Å3Block, red
Z = 40.23 × 0.21 × 0.19 mm
Data collection top
Bruker APEXII CCD
diffractometer
2857 independent reflections
Radiation source: fine-focus sealed tube1596 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.031
ϕ and ω scansθmax = 25.5°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
h = 2727
Tmin = 0.985, Tmax = 0.987k = 1010
10667 measured reflectionsl = 2220
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)] = 0.059Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.211H-atom parameters constrained
S = 1.16 w = 1/[σ2(Fo2) + (0.0705P)2 + 3.4006P]
where P = (Fo2 + 2Fc2)/3
2857 reflections(Δ/σ)max < 0.001
193 parametersΔρmax = 0.23 e Å3
0 restraintsΔρmin = 0.20 e Å3
Crystal data top
C40H32N2V = 3082 (4) Å3
Mr = 540.68Z = 4
Monoclinic, C2/cMo Kα radiation
a = 22.994 (14) ŵ = 0.07 mm1
b = 8.676 (5) ÅT = 296 K
c = 18.652 (18) Å0.23 × 0.21 × 0.19 mm
β = 124.084 (4)°
Data collection top
Bruker APEXII CCD
diffractometer
2857 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2008a)
1596 reflections with I > 2σ(I)
Tmin = 0.985, Tmax = 0.987Rint = 0.031
10667 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0590 restraints
wR(F2) = 0.211H-atom parameters constrained
S = 1.16Δρmax = 0.23 e Å3
2857 reflectionsΔρmin = 0.20 e Å3
193 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
C10.2760 (2)0.8437 (6)0.7549 (2)0.1024 (15)
H10.24110.76990.73680.123*
C20.3295 (3)0.8543 (8)0.8419 (3)0.132 (2)
H20.33030.78770.88150.159*
C30.3807 (3)0.9614 (9)0.8696 (3)0.135 (3)
H30.41580.97050.92830.162*
C40.3807 (2)1.0559 (8)0.8112 (4)0.126 (2)
H40.41651.12780.83000.151*
C50.3271 (2)1.0452 (6)0.7229 (3)0.1089 (16)
H50.32771.10890.68320.131*
C60.27359 (18)0.9396 (5)0.6951 (2)0.0804 (11)
C70.21565 (18)0.9254 (4)0.6012 (2)0.0691 (9)
C80.22787 (19)0.9461 (4)0.5373 (2)0.0719 (10)
H80.27290.97260.55340.086*
C90.1758 (2)0.9289 (4)0.4504 (2)0.0707 (10)
C100.10860 (19)0.8859 (3)0.42739 (19)0.0639 (9)
C110.09402 (17)0.8687 (4)0.4894 (2)0.0668 (9)
C120.14776 (18)0.8885 (4)0.5757 (2)0.0720 (10)
H120.13820.87680.61770.086*
C130.02861 (17)0.7530 (3)0.29823 (18)0.0617 (9)
C140.04351 (15)0.5886 (3)0.32523 (18)0.0526 (8)
C150.00000.5015 (4)0.25000.0497 (10)
C160.00000.3396 (5)0.25000.0642 (12)
C170.0457 (2)0.2681 (4)0.3300 (2)0.0833 (12)
H170.04760.16100.33340.100*
C180.08782 (19)0.3537 (4)0.4034 (2)0.0753 (10)
H180.11770.30280.45550.090*
C190.08738 (16)0.5154 (3)0.4025 (2)0.0619 (9)
H190.11620.57120.45320.074*
C200.1907 (3)0.9524 (5)0.3822 (2)0.1042 (15)
H20A0.23760.99080.40880.156*
H20B0.15791.02530.34020.156*
H20C0.18610.85590.35420.156*
C210.02117 (19)0.8275 (5)0.4649 (3)0.0984 (14)
H21A0.01230.89740.42120.148*
H21B0.01940.83500.51510.148*
H21C0.01010.72400.44300.148*
N10.05454 (16)0.8787 (3)0.33777 (16)0.0755 (9)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.081 (3)0.157 (4)0.056 (2)0.001 (3)0.030 (2)0.013 (3)
C20.095 (3)0.217 (7)0.060 (3)0.012 (4)0.028 (3)0.017 (3)
C30.071 (3)0.239 (7)0.071 (3)0.023 (4)0.025 (3)0.055 (4)
C40.070 (3)0.205 (6)0.098 (4)0.027 (3)0.044 (3)0.082 (4)
C50.080 (3)0.158 (5)0.082 (3)0.031 (3)0.041 (2)0.059 (3)
C60.064 (2)0.113 (3)0.060 (2)0.005 (2)0.0321 (19)0.030 (2)
C70.070 (2)0.074 (2)0.054 (2)0.0068 (17)0.0291 (18)0.0192 (17)
C80.077 (2)0.070 (2)0.063 (2)0.0172 (18)0.0356 (19)0.0174 (17)
C90.095 (3)0.0485 (18)0.058 (2)0.0117 (18)0.036 (2)0.0076 (15)
C100.084 (2)0.0305 (15)0.0465 (19)0.0000 (15)0.0174 (18)0.0051 (12)
C110.063 (2)0.0528 (19)0.060 (2)0.0019 (15)0.0198 (17)0.0129 (15)
C120.067 (2)0.082 (2)0.059 (2)0.0036 (18)0.0293 (18)0.0152 (17)
C130.080 (2)0.0283 (15)0.0504 (17)0.0004 (14)0.0208 (16)0.0002 (12)
C140.0646 (18)0.0322 (15)0.0498 (17)0.0021 (13)0.0252 (15)0.0007 (12)
C150.063 (2)0.0282 (19)0.051 (2)0.0000.027 (2)0.000
C160.078 (3)0.036 (2)0.064 (3)0.0000.031 (3)0.000
C170.102 (3)0.0344 (17)0.087 (3)0.0073 (17)0.036 (2)0.0108 (17)
C180.086 (2)0.050 (2)0.065 (2)0.0111 (17)0.0268 (19)0.0197 (17)
C190.073 (2)0.0420 (17)0.0547 (19)0.0052 (15)0.0257 (17)0.0054 (14)
C200.145 (4)0.091 (3)0.073 (3)0.020 (3)0.059 (3)0.001 (2)
C210.067 (2)0.105 (3)0.091 (3)0.003 (2)0.025 (2)0.028 (2)
N10.100 (2)0.0295 (13)0.0510 (16)0.0021 (13)0.0140 (15)0.0045 (11)
Geometric parameters (Å, º) top
C1—C61.368 (6)C12—H120.9300
C1—C21.386 (6)C13—N11.263 (4)
C1—H10.9300C13—C141.487 (4)
C2—C31.355 (8)C13—C13i1.522 (6)
C2—H20.9300C14—C191.368 (4)
C3—C41.363 (8)C14—C151.403 (3)
C3—H30.9300C15—C14i1.403 (3)
C4—C51.402 (6)C15—C161.404 (6)
C4—H40.9300C16—C17i1.400 (4)
C5—C61.381 (6)C16—C171.400 (4)
C5—H50.9300C17—C181.370 (5)
C6—C71.497 (5)C17—H170.9300
C7—C81.381 (5)C18—C191.403 (4)
C7—C121.391 (5)C18—H180.9300
C8—C91.382 (4)C19—H190.9300
C8—H80.9300C20—H20A0.9600
C9—C101.404 (5)C20—H20B0.9600
C9—C201.504 (5)C20—H20C0.9600
C10—C111.381 (5)C21—H21A0.9600
C10—N11.419 (4)C21—H21B0.9600
C11—C121.385 (4)C21—H21C0.9600
C11—C211.512 (5)
C6—C1—C2121.2 (5)C7—C12—H12119.2
C6—C1—H1119.4N1—C13—C14133.3 (3)
C2—C1—H1119.4N1—C13—C13i120.18 (17)
C3—C2—C1120.3 (6)C14—C13—C13i106.44 (15)
C3—C2—H2119.9C19—C14—C15119.7 (3)
C1—C2—H2119.9C19—C14—C13134.2 (3)
C2—C3—C4119.8 (5)C15—C14—C13106.2 (2)
C2—C3—H3120.1C14i—C15—C14114.8 (3)
C4—C3—H3120.1C14i—C15—C16122.62 (17)
C3—C4—C5120.4 (5)C14—C15—C16122.62 (17)
C3—C4—H4119.8C17i—C16—C17127.3 (4)
C5—C4—H4119.8C17i—C16—C15116.3 (2)
C6—C5—C4119.8 (5)C17—C16—C15116.3 (2)
C6—C5—H5120.1C18—C17—C16120.8 (3)
C4—C5—H5120.1C18—C17—H17119.6
C1—C6—C5118.5 (4)C16—C17—H17119.6
C1—C6—C7120.4 (4)C17—C18—C19122.3 (3)
C5—C6—C7121.1 (4)C17—C18—H18118.8
C8—C7—C12117.9 (3)C19—C18—H18118.8
C8—C7—C6121.4 (3)C14—C19—C18118.2 (3)
C12—C7—C6120.8 (3)C14—C19—H19120.9
C9—C8—C7122.5 (3)C18—C19—H19120.9
C9—C8—H8118.7C9—C20—H20A109.5
C7—C8—H8118.7C9—C20—H20B109.5
C8—C9—C10117.9 (3)H20A—C20—H20B109.5
C8—C9—C20121.3 (4)C9—C20—H20C109.5
C10—C9—C20120.8 (3)H20A—C20—H20C109.5
C11—C10—C9121.0 (3)H20B—C20—H20C109.5
C11—C10—N1121.2 (3)C11—C21—H21A109.5
C9—C10—N1117.3 (3)C11—C21—H21B109.5
C10—C11—C12118.9 (3)H21A—C21—H21B109.5
C10—C11—C21121.4 (3)C11—C21—H21C109.5
C12—C11—C21119.7 (4)H21A—C21—H21C109.5
C11—C12—C7121.7 (3)H21B—C21—H21C109.5
C11—C12—H12119.2C13—N1—C10122.7 (2)
C6—C1—C2—C30.3 (8)C21—C11—C12—C7179.6 (3)
C1—C2—C3—C42.0 (8)C8—C7—C12—C111.7 (5)
C2—C3—C4—C51.5 (8)C6—C7—C12—C11177.3 (3)
C3—C4—C5—C60.8 (7)N1—C13—C14—C194.2 (7)
C2—C1—C6—C52.0 (7)C13i—C13—C14—C19178.1 (4)
C2—C1—C6—C7179.5 (4)N1—C13—C14—C15176.1 (4)
C4—C5—C6—C12.5 (6)C13i—C13—C14—C151.6 (4)
C4—C5—C6—C7180.0 (4)C19—C14—C15—C14i179.1 (3)
C1—C6—C7—C8142.6 (4)C13—C14—C15—C14i0.65 (17)
C5—C6—C7—C834.9 (5)C19—C14—C15—C160.9 (3)
C1—C6—C7—C1236.4 (5)C13—C14—C15—C16179.35 (17)
C5—C6—C7—C12146.1 (4)C14i—C15—C16—C17i0.5 (2)
C12—C7—C8—C91.1 (5)C14—C15—C16—C17i179.5 (2)
C6—C7—C8—C9177.9 (3)C14i—C15—C16—C17179.5 (2)
C7—C8—C9—C101.3 (5)C14—C15—C16—C170.5 (2)
C7—C8—C9—C20179.9 (3)C17i—C16—C17—C18179.8 (4)
C8—C9—C10—C113.2 (5)C15—C16—C17—C180.2 (4)
C20—C9—C10—C11178.0 (3)C16—C17—C18—C190.1 (6)
C8—C9—C10—N1175.9 (3)C15—C14—C19—C180.8 (5)
C20—C9—C10—N15.3 (5)C13—C14—C19—C18179.5 (4)
C9—C10—C11—C122.7 (5)C17—C18—C19—C140.5 (6)
N1—C10—C11—C12175.1 (3)C14—C13—N1—C101.7 (7)
C9—C10—C11—C21177.9 (3)C13i—C13—N1—C10179.2 (4)
N1—C10—C11—C215.5 (5)C11—C10—N1—C1378.7 (5)
C10—C11—C12—C70.2 (5)C9—C10—N1—C13108.6 (4)
Symmetry code: (i) x, y, z+1/2.

Experimental details

Crystal data
Chemical formulaC40H32N2
Mr540.68
Crystal system, space groupMonoclinic, C2/c
Temperature (K)296
a, b, c (Å)22.994 (14), 8.676 (5), 18.652 (18)
β (°) 124.084 (4)
V3)3082 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.07
Crystal size (mm)0.23 × 0.21 × 0.19
Data collection
DiffractometerBruker APEXII CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2008a)
Tmin, Tmax0.985, 0.987
No. of measured, independent and
observed [I > 2σ(I)] reflections
10667, 2857, 1596
Rint0.031
(sin θ/λ)max1)0.606
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.059, 0.211, 1.16
No. of reflections2857
No. of parameters193
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.23, 0.20

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

 

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 the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province (Northwest Normal University), for financial support.

References

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Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
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