organic compounds
2,3-Bis[(3-methylbiphenyl-4-yl)imino]butane
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
The title compound, C30H28N2, is a product of the condensation reaction of 2-methyl-4-phenylaniline and butane-2,3-dione. The molecule lies on a crystallographic inversion centre. The C=N bond has an E conformation. The dihedral angle between the two benzene rings of the 4-phenyl-2-methylphenyl group is 29.19 (76)°. The 1,4-diazabutadiene plane makes an angle of 70.1 (10)° with the N-bonded methylphenyl ring and an angle of 81.08 (97)° with the terminal phenyl group.
CCDC reference: 991458
Related literature
The title compound was synthesized as an α-diimine ligand for applications in olefin polymerization Ni(II)-α-diimine catalysts, see: Johnson et al. (1995); Killian et al. (1996); Wang et al. (2013); Ionkin & Marshall (2004); Meinhard et al. (2007). For the effect of the ligand structure on the activity of the catalyst and the properties of the products, see: Popeney & Guan (2005); Yuan et al. (2005); Helldörfer et al. (2003). For related structures, see: Yuan et al. (2013).
Experimental
Crystal data
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Data collection: APEX2 (Bruker, 2008); cell SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
CCDC reference: 991458
10.1107/S1600536814005686/fk2080sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814005686/fk2080Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814005686/fk2080Isup3.cml
Formic acid (0.5 ml) was added to a stirred solution of 2-methyl-4-phenylaniline (0.916 g, 2.2 mmol) and 2,3-Butanedione (0.086 g, 1 mmol) in 20 ml anhydrous ethanol (20 ml). The mixture was stirred at 50 oC for 24 h, then cooled, and the precipitate was separated by filtration. The solid was recrystallized from ethanol/dichloromethane (v/v= 8:1), washed with cold ethanol and dried under vacuum to give the title compound. Yield is 86%. Crystals suitable for X-ray
were grown from a cyclohexane/dichloromethane (v:v= 1:2) solution. Anal. Calc. for C30H28N2: C, 86.50; H, 6.78; N, 6.72. Found: C, 86.62; H, 6.57; N, 6.58.Positions of the methyl H atoms were derived from Fourier maps (HFIX 137), with C–H 0.96 Å and Uiso(H) = 1.5Ueq(C). All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms with C–H distances distances of 0.93 Å and Uiso(H) = 1.2Ueq(C).
Data collection: APEX2 (Bruker, 2008); cell
SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C30H28N2 | Dx = 1.175 Mg m−3 |
Mr = 416.54 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pbca | Cell parameters from 1674 reflections |
a = 8.347 (3) Å | θ = 2.6–21.7° |
b = 7.063 (3) Å | µ = 0.07 mm−1 |
c = 39.946 (16) Å | T = 293 K |
V = 2355.0 (16) Å3 | Block, yellow |
Z = 4 | 0.19 × 0.18 × 0.15 mm |
F(000) = 888 |
Bruker APEXII CCD diffractometer | 2200 independent reflections |
Radiation source: fine-focus sealed tube | 1251 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.088 |
ϕ and ω scans | θmax = 25.5°, θmin = 2.6° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −10→10 |
Tmin = 0.987, Tmax = 0.990 | k = −8→8 |
15668 measured reflections | l = −48→47 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.069 | H-atom parameters constrained |
wR(F2) = 0.135 | w = 1/[σ2(Fo2) + (0.0366P)2 + 1.4273P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
2200 reflections | Δρmax = 0.15 e Å−3 |
148 parameters | Δρmin = −0.16 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0025 (6) |
C30H28N2 | V = 2355.0 (16) Å3 |
Mr = 416.54 | Z = 4 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 8.347 (3) Å | µ = 0.07 mm−1 |
b = 7.063 (3) Å | T = 293 K |
c = 39.946 (16) Å | 0.19 × 0.18 × 0.15 mm |
Bruker APEXII CCD diffractometer | 2200 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 1251 reflections with I > 2σ(I) |
Tmin = 0.987, Tmax = 0.990 | Rint = 0.088 |
15668 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.135 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.15 e Å−3 |
2200 reflections | Δρmin = −0.16 e Å−3 |
148 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
C1 | 0.6218 (4) | −0.0240 (5) | 0.17712 (7) | 0.0644 (9) | |
H1 | 0.7117 | −0.0468 | 0.1640 | 0.077* | |
C2 | 0.6029 (4) | −0.1219 (5) | 0.20680 (8) | 0.0716 (10) | |
H2 | 0.6792 | −0.2106 | 0.2133 | 0.086* | |
C3 | 0.4725 (4) | −0.0893 (5) | 0.22677 (7) | 0.0663 (9) | |
H3 | 0.4597 | −0.1548 | 0.2468 | 0.080* | |
C4 | 0.3612 (4) | 0.0413 (4) | 0.21680 (7) | 0.0594 (9) | |
H4 | 0.2726 | 0.0652 | 0.2303 | 0.071* | |
C5 | 0.3788 (4) | 0.1375 (4) | 0.18713 (6) | 0.0504 (8) | |
H5 | 0.3012 | 0.2248 | 0.1807 | 0.061* | |
C6 | 0.5099 (3) | 0.1070 (4) | 0.16654 (6) | 0.0442 (7) | |
C7 | 0.5276 (3) | 0.2107 (4) | 0.13451 (6) | 0.0425 (7) | |
C8 | 0.6072 (3) | 0.1298 (4) | 0.10744 (7) | 0.0509 (8) | |
H8 | 0.6563 | 0.0124 | 0.1099 | 0.061* | |
C9 | 0.6142 (3) | 0.2216 (4) | 0.07704 (7) | 0.0532 (8) | |
H9 | 0.6678 | 0.1652 | 0.0592 | 0.064* | |
C10 | 0.5427 (3) | 0.3961 (4) | 0.07266 (6) | 0.0423 (7) | |
C11 | 0.4688 (3) | 0.4856 (4) | 0.09956 (6) | 0.0432 (7) | |
C12 | 0.4629 (3) | 0.3887 (4) | 0.12980 (6) | 0.0443 (7) | |
H12 | 0.4126 | 0.4468 | 0.1479 | 0.053* | |
C13 | 0.3949 (4) | 0.6774 (4) | 0.09594 (8) | 0.0674 (10) | |
H13A | 0.2882 | 0.6648 | 0.0873 | 0.101* | |
H13B | 0.4580 | 0.7522 | 0.0808 | 0.101* | |
H13C | 0.3912 | 0.7384 | 0.1174 | 0.101* | |
C14 | 0.4850 (3) | 0.4425 (4) | 0.01552 (6) | 0.0440 (7) | |
C15 | 0.3729 (4) | 0.2792 (5) | 0.01278 (8) | 0.0773 (11) | |
H15A | 0.3722 | 0.2102 | 0.0335 | 0.116* | |
H15B | 0.4073 | 0.1972 | −0.0050 | 0.116* | |
H15C | 0.2670 | 0.3248 | 0.0081 | 0.116* | |
N1 | 0.5572 (3) | 0.4954 (3) | 0.04174 (5) | 0.0486 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.068 (2) | 0.078 (3) | 0.0472 (19) | 0.013 (2) | 0.0012 (16) | 0.0083 (18) |
C2 | 0.086 (3) | 0.075 (2) | 0.054 (2) | 0.016 (2) | −0.0096 (19) | 0.012 (2) |
C3 | 0.092 (3) | 0.064 (2) | 0.0429 (18) | −0.005 (2) | −0.0080 (19) | 0.0083 (17) |
C4 | 0.075 (2) | 0.063 (2) | 0.0400 (17) | −0.0046 (19) | 0.0066 (16) | −0.0005 (16) |
C5 | 0.0651 (19) | 0.0476 (19) | 0.0386 (17) | −0.0013 (16) | 0.0034 (14) | 0.0006 (15) |
C6 | 0.0502 (17) | 0.0475 (18) | 0.0349 (15) | 0.0018 (15) | −0.0037 (13) | −0.0025 (14) |
C7 | 0.0388 (15) | 0.0504 (19) | 0.0381 (16) | −0.0011 (15) | −0.0014 (13) | −0.0022 (14) |
C8 | 0.0587 (18) | 0.0529 (19) | 0.0410 (17) | 0.0119 (16) | 0.0057 (14) | 0.0047 (16) |
C9 | 0.0593 (18) | 0.058 (2) | 0.0424 (18) | 0.0049 (17) | 0.0088 (15) | −0.0019 (16) |
C10 | 0.0417 (15) | 0.0495 (18) | 0.0356 (16) | −0.0052 (15) | −0.0010 (13) | 0.0013 (14) |
C11 | 0.0430 (15) | 0.0456 (17) | 0.0410 (17) | −0.0007 (14) | −0.0023 (13) | −0.0011 (14) |
C12 | 0.0474 (16) | 0.0479 (18) | 0.0377 (16) | 0.0014 (15) | 0.0034 (13) | −0.0058 (14) |
C13 | 0.088 (2) | 0.055 (2) | 0.059 (2) | 0.0099 (19) | 0.0034 (18) | 0.0063 (17) |
C14 | 0.0404 (15) | 0.0522 (19) | 0.0395 (16) | −0.0047 (14) | 0.0022 (13) | 0.0024 (13) |
C15 | 0.090 (2) | 0.086 (3) | 0.055 (2) | −0.041 (2) | −0.0109 (19) | 0.0185 (19) |
N1 | 0.0521 (14) | 0.0561 (16) | 0.0375 (13) | −0.0075 (12) | 0.0012 (12) | 0.0028 (12) |
C1—C6 | 1.381 (4) | C9—C10 | 1.380 (4) |
C1—C2 | 1.382 (4) | C9—H9 | 0.9300 |
C1—H1 | 0.9300 | C10—C11 | 1.391 (3) |
C2—C3 | 1.369 (4) | C10—N1 | 1.426 (3) |
C2—H2 | 0.9300 | C11—C12 | 1.389 (3) |
C3—C4 | 1.368 (4) | C11—C13 | 1.496 (4) |
C3—H3 | 0.9300 | C12—H12 | 0.9300 |
C4—C5 | 1.374 (4) | C13—H13A | 0.9600 |
C4—H4 | 0.9300 | C13—H13B | 0.9600 |
C5—C6 | 1.386 (4) | C13—H13C | 0.9600 |
C5—H5 | 0.9300 | C14—N1 | 1.265 (3) |
C6—C7 | 1.481 (4) | C14—C15 | 1.489 (4) |
C7—C12 | 1.381 (4) | C14—C14i | 1.504 (5) |
C7—C8 | 1.392 (3) | C15—H15A | 0.9600 |
C8—C9 | 1.378 (4) | C15—H15B | 0.9600 |
C8—H8 | 0.9300 | C15—H15C | 0.9600 |
C6—C1—C2 | 121.4 (3) | C8—C9—H9 | 119.6 |
C6—C1—H1 | 119.3 | C9—C10—C11 | 120.0 (3) |
C2—C1—H1 | 119.3 | C9—C10—N1 | 120.8 (2) |
C3—C2—C1 | 120.4 (3) | C11—C10—N1 | 118.9 (3) |
C3—C2—H2 | 119.8 | C10—C11—C12 | 117.6 (3) |
C1—C2—H2 | 119.8 | C10—C11—C13 | 121.3 (3) |
C4—C3—C2 | 118.9 (3) | C12—C11—C13 | 121.1 (3) |
C4—C3—H3 | 120.5 | C7—C12—C11 | 123.6 (3) |
C2—C3—H3 | 120.5 | C7—C12—H12 | 118.2 |
C3—C4—C5 | 120.8 (3) | C11—C12—H12 | 118.2 |
C3—C4—H4 | 119.6 | C11—C13—H13A | 109.5 |
C5—C4—H4 | 119.6 | C11—C13—H13B | 109.5 |
C4—C5—C6 | 121.3 (3) | H13A—C13—H13B | 109.5 |
C4—C5—H5 | 119.4 | C11—C13—H13C | 109.5 |
C6—C5—H5 | 119.4 | H13A—C13—H13C | 109.5 |
C1—C6—C5 | 117.2 (3) | H13B—C13—H13C | 109.5 |
C1—C6—C7 | 121.9 (3) | N1—C14—C15 | 126.1 (3) |
C5—C6—C7 | 120.9 (3) | N1—C14—C14i | 116.4 (3) |
C12—C7—C8 | 117.0 (3) | C15—C14—C14i | 117.5 (3) |
C12—C7—C6 | 121.9 (3) | C14—C15—H15A | 109.5 |
C8—C7—C6 | 121.1 (3) | C14—C15—H15B | 109.5 |
C9—C8—C7 | 120.8 (3) | H15A—C15—H15B | 109.5 |
C9—C8—H8 | 119.6 | C14—C15—H15C | 109.5 |
C7—C8—H8 | 119.6 | H15A—C15—H15C | 109.5 |
C10—C9—C8 | 120.9 (3) | H15B—C15—H15C | 109.5 |
C10—C9—H9 | 119.6 | C14—N1—C10 | 122.1 (2) |
C6—C1—C2—C3 | −0.8 (5) | C8—C9—C10—C11 | 3.0 (4) |
C1—C2—C3—C4 | 0.2 (5) | C8—C9—C10—N1 | 176.7 (3) |
C2—C3—C4—C5 | 0.5 (5) | C9—C10—C11—C12 | −3.4 (4) |
C3—C4—C5—C6 | −0.6 (5) | N1—C10—C11—C12 | −177.2 (2) |
C2—C1—C6—C5 | 0.7 (5) | C9—C10—C11—C13 | 178.0 (3) |
C2—C1—C6—C7 | −179.0 (3) | N1—C10—C11—C13 | 4.2 (4) |
C4—C5—C6—C1 | 0.0 (4) | C8—C7—C12—C11 | 2.3 (4) |
C4—C5—C6—C7 | 179.7 (3) | C6—C7—C12—C11 | −176.1 (3) |
C1—C6—C7—C12 | −152.1 (3) | C10—C11—C12—C7 | 0.7 (4) |
C5—C6—C7—C12 | 28.3 (4) | C13—C11—C12—C7 | 179.4 (3) |
C1—C6—C7—C8 | 29.6 (4) | C15—C14—N1—C10 | 2.3 (5) |
C5—C6—C7—C8 | −150.0 (3) | C14i—C14—N1—C10 | −178.4 (3) |
C12—C7—C8—C9 | −2.7 (4) | C9—C10—N1—C14 | 71.9 (4) |
C6—C7—C8—C9 | 175.7 (3) | C11—C10—N1—C14 | −114.4 (3) |
C7—C8—C9—C10 | 0.1 (4) |
Symmetry code: (i) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C30H28N2 |
Mr | 416.54 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 8.347 (3), 7.063 (3), 39.946 (16) |
V (Å3) | 2355.0 (16) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.19 × 0.18 × 0.15 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.987, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15668, 2200, 1251 |
Rint | 0.088 |
(sin θ/λ)max (Å−1) | 0.605 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.135, 1.01 |
No. of reflections | 2200 |
No. of parameters | 148 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.16 |
Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 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 the Ministry of Education, Key Laboratory of Polymer Materials of Gansu Province (Northwest Normal University), for financial support.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
In recent years, a variety of α-diimine ligands containing various ortho and para position substituted N-aryl rings (Johnson et al. 1995; Killian et al.. 1996; Popeney et al.. 2005; Yuan et al., 2005; Wang et al. 2013) and backbone effects (Helldörfer et al.. 2003) and teraryl substituted-α-diimine ligands (Ionkin et al.. 2004; Meinhard et al.. 2007) were employed to study their influence on the catalytic activity of α-diimine-Ni(II) complexes. In this study, we designed and synthesized the title compound as a bidentate ligand. The molecule lies on a crystallographic inversion centre. The single bond of 1, 4-diazabutadiene fragment is (E)-configured. The dihedral angles between the 1,4-diazabutadiene plane and the benzene ring bonded to the N atom are 70.12 (96)° and 81.08 (97)° for the terminal phenyl group, resp. The dihedral angle between both aromatic ring planes is 29.19 (76)° (Figure 1). The crystal packing shows stacking of molecules along a-axis (Figure 2), however, no significant intermolecular H-bonding is observed. A very similar molecular structure is known from Yuan et al. (2013).