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Acta Cryst. (2007). E63, m2549    [ doi:10.1107/S1600536807044388 ]

{N-[2-(2,6-Dimethylphenylamino)benzylidene]-2,6-dimethylaniline-[kappa]2N,N'}dimethylaluminium(III)

X.-M. Liu, W. Gao, B. Li, J.-G. Ni and Y. Mu

Abstract top

In the title complex, [Al(CH3)2(C23H23N2)], a mononuclear Schiff base dimethylaluminium complex, the Al atom is four-coordinated by two N atoms from one Schiff base ligand and by the C atoms of the two methyl substituents. The Al atom exhibits a distorted tetrahedral coordination geometry.

Comment top

Organoaluminium complexes are currently generating considerable interest due to their increasing role in polymerization chemistry, such as cationic (Bochmann & Dawson, 1996), anionic (Kuroki et al., 1991) and ring-opening polymerization, (Jegier & Atwood, 1997) and as cocatalysts in transition metal-catalysed olefin polymerization (McKnight & Waymouth, 1998; Britovsek et al., 1999). Previously, a lot of alkylaluminium complexes with bidentate (Gameron et al., 2001; Pappalardo et al., 2002) or tridentate (Gameron et al., 1999; Huang et al., 2001) Schiff base ligands have been reported. Our current research efforts are focused on alkylaluminium complexes with new ligands. Herein we report the structure of the title complex, a mononuclear Schiff base dimethyl aluminium complex.

An ORTEP drawing of the molecular structure of the complex is shown in Fig. 1. The aluminium atom exhibits a distorted tetrahedral geometry. The N—Al—N angle (93.8°) in the complex is similar to that of ortho-C6H4N(C6H4-4-Me)(CH=NC6H4-4-Me)AlMe2 (94.5°, Liu et al., 2005), but larger than those in {tBuC(NCy)2}AlMe2 (Coles et al., 1997) and {(iPr)2ATI}AlMe2 (Dias et al., 1995) with four- and five- membered chelating rings, which exhibit angles of 69° and 84°, respectively. In the title compound the six membered chelating ring is nearly planar and the distance of the aluminium atom from the mean plane made up by the other five atoms of the six membered ring is only 0.1383 (7) Å. The imino C=N bond in the complex retains its double bond character with a bond length of 1.295 (2) Å.

Related literature top

For related literature, see: Bochmann & Dawson (1996); Britovsek et al. (1999); Coles et al. (1997); Dias et al. (1995); Gameron et al. (1999, 2001); Huang et al. (2001); Jegier & Atwood (1997); Kuroki et al. (1991); Liu et al. (2005); Pappalardo et al. (2002); McKnight & Waymouth (1998).

Experimental top

A solution of ortho-C6H4NH(C6H3-2,6-Me2)(CH=NC6H3-2,6-Me2) (0.20 g, 0.61 mmol) (Liu et al., 2005) in 10 ml of n-hexane was slowly added to a solution of AlMe3 (0.61 mmol) in 15 ml of n-hexane at 273 K with stirring. The mixture was stirred at 273 K for 30 min, and at room temperature for additional 2 h, was then concentrated to about 10 ml and kept at 253 K overnight to let the product crystallize. The product was obtained as orange-green crystals (0.21 g, 90%).

Refinement top

The C-bound H atoms were positioned geometrically with C—H = 0.93–0.96 Å, and allowed to ride on their parent atoms with Uiso(H) = 1.5Ueq(C) for methyl and 1.2Ueq(C) for all other hydrogen atoms.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures top
[Figure 1] Fig. 1. View of the molecule of the title compound showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen atoms were omitted for clarity.
{N-[2-(2,6-Dimethylphenylamino)benzylidene]-2,6-dimethylaniline- κ2N,N'}dimethylaluminium(III) top
Crystal data top
[Al(CH3)2(C23H23N2)]F000 = 824
Mr = 384.48Dx = 1.136 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 11340 reflections
a = 9.0483 (18) Åθ = 5.8–54.9º
b = 11.045 (2) ŵ = 0.10 mm−1
c = 24.192 (5) ÅT = 293 (2) K
β = 111.64 (3)ºBlock, yellow
V = 2247.3 (8) Å30.19 × 0.18 × 0.15 mm
Z = 4
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5115 independent reflections
Radiation source: fine-focus sealed tube2682 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.043
T = 293(2) Kθmax = 27.5º
ω scansθmin = 1.8º
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		h = −11→11
Tmin = 0.981, Tmax = 0.985k = −14→14
11340 measured reflectionsl = −28→31
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.047H-atom parameters constrained
wR(F2) = 0.106  w = 1/[σ2(Fo2) + (0.0378P)2]
where P = (Fo2 + 2Fc2)/3
S = 0.96(Δ/σ)max = 0.002
5115 reflectionsΔρmax = 0.16 e Å−3
259 parametersΔρmin = −0.18 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[Al(CH3)2(C23H23N2)]V = 2247.3 (8) Å3
Mr = 384.48Z = 4
Monoclinic, P21/cMo Kα
a = 9.0483 (18) ŵ = 0.10 mm−1
b = 11.045 (2) ÅT = 293 (2) K
c = 24.192 (5) Å0.19 × 0.18 × 0.15 mm
β = 111.64 (3)º
Data collection top
Rigaku R-AXIS RAPID
diffractometer		5115 independent reflections
Absorption correction: multi-scan
(ABSCOR; Higashi, 1995)		2682 reflections with I > 2σ(I)
Tmin = 0.981, Tmax = 0.985Rint = 0.043
11340 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.047259 parameters
wR(F2) = 0.106H-atom parameters constrained
S = 0.96Δρmax = 0.16 e Å−3
5115 reflectionsΔρmin = −0.18 e Å−3
Special details top

Experimental. (See detailed section in the paper)

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
Al10.26222 (6)0.28378 (5)0.10575 (2)0.04098 (16)
N10.41224 (16)0.39710 (13)0.15157 (6)0.0402 (4)
N20.39168 (17)0.23307 (13)0.06112 (6)0.0405 (4)
C10.5702 (2)0.40123 (15)0.16054 (7)0.0388 (4)
C20.6757 (2)0.47997 (17)0.20191 (8)0.0499 (5)
H20.63700.53230.22350.060*
C30.8334 (2)0.48160 (19)0.21122 (9)0.0563 (5)
H30.90010.53420.23950.068*
C40.8975 (2)0.40686 (19)0.17966 (9)0.0600 (6)
H41.00570.40850.18670.072*
C50.7995 (2)0.33225 (18)0.13870 (9)0.0539 (5)
H50.84130.28250.11710.065*
C60.6352 (2)0.32662 (16)0.12728 (8)0.0410 (4)
C70.5424 (2)0.25570 (16)0.07846 (8)0.0466 (5)
H70.59560.22100.05600.056*
C80.3519 (2)0.48571 (17)0.18158 (8)0.0435 (5)
C90.3534 (2)0.4627 (2)0.23841 (9)0.0545 (5)
C100.2850 (3)0.5477 (3)0.26395 (11)0.0775 (8)
H100.28530.53470.30200.093*
C110.2172 (3)0.6506 (3)0.23360 (15)0.0872 (9)
H110.16940.70570.25090.105*
C120.2188 (3)0.6734 (2)0.17843 (14)0.0799 (8)
H120.17240.74390.15850.096*
C130.2891 (2)0.59224 (18)0.15176 (10)0.0582 (6)
C140.4301 (3)0.3531 (2)0.27284 (9)0.0817 (7)
H14A0.43460.29060.24590.123*
H14B0.36910.32520.29550.123*
H14C0.53590.37280.29930.123*
C150.3006 (3)0.6233 (2)0.09329 (11)0.0847 (8)
H15A0.23230.69070.07590.127*
H15B0.26850.55480.06710.127*
H15C0.40840.64420.09930.127*
C160.3169 (2)0.17614 (18)0.00394 (9)0.0485 (5)
C170.2837 (3)0.0534 (2)0.00084 (11)0.0667 (6)
C180.1980 (3)0.0062 (3)−0.05477 (15)0.0936 (9)
H180.1706−0.0754−0.05830.112*
C190.1535 (3)0.0758 (4)−0.10386 (15)0.1062 (12)
H190.09490.0419−0.14060.127*
C200.1932 (3)0.1959 (3)−0.10033 (11)0.0879 (8)
H200.16430.2422−0.13480.106*
C210.2751 (3)0.2486 (2)−0.04632 (9)0.0607 (6)
C220.3397 (4)−0.0260 (2)0.05438 (13)0.1026 (10)
H22A0.37670.02320.08960.154*
H22B0.4250−0.07630.05310.154*
H22C0.2535−0.07610.05490.154*
C230.3145 (3)0.3815 (2)−0.04262 (11)0.0872 (8)
H23A0.26510.4178−0.08110.131*
H23B0.42770.3916−0.02940.131*
H23C0.27600.4199−0.01500.131*
C240.0638 (2)0.35035 (19)0.05008 (9)0.0601 (6)
H24A0.01940.40490.07070.090*
H24B−0.00980.28570.03300.090*
H24C0.08410.39320.01910.090*
C250.2286 (3)0.15255 (19)0.15330 (9)0.0702 (6)
H25A0.32930.11840.17750.105*
H25B0.16380.09120.12750.105*
H25C0.17610.18320.17840.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Al10.0376 (3)0.0463 (3)0.0386 (3)−0.0041 (3)0.0135 (2)0.0009 (3)
N10.0371 (8)0.0443 (9)0.0402 (9)−0.0009 (7)0.0156 (7)−0.0046 (7)
N20.0405 (8)0.0392 (9)0.0421 (9)−0.0055 (7)0.0157 (7)−0.0019 (7)
C10.0395 (10)0.0405 (10)0.0336 (10)−0.0042 (9)0.0101 (8)0.0022 (8)
C20.0459 (12)0.0568 (12)0.0485 (12)−0.0062 (10)0.0189 (10)−0.0105 (10)
C30.0451 (12)0.0671 (14)0.0543 (13)−0.0140 (11)0.0156 (10)−0.0128 (11)
C40.0416 (11)0.0752 (15)0.0658 (14)−0.0104 (11)0.0230 (11)−0.0070 (12)
C50.0461 (12)0.0606 (13)0.0611 (13)−0.0036 (10)0.0268 (10)−0.0095 (11)
C60.0388 (10)0.0452 (11)0.0427 (11)−0.0041 (9)0.0194 (9)−0.0028 (9)
C70.0516 (12)0.0442 (11)0.0501 (12)−0.0008 (9)0.0258 (10)−0.0031 (9)
C80.0316 (10)0.0481 (11)0.0469 (12)−0.0040 (9)0.0100 (8)−0.0101 (10)
C90.0418 (11)0.0733 (14)0.0497 (12)−0.0071 (11)0.0183 (10)−0.0194 (12)
C100.0575 (15)0.110 (2)0.0721 (17)−0.0199 (15)0.0314 (13)−0.0425 (16)
C110.0515 (15)0.088 (2)0.127 (3)−0.0092 (14)0.0383 (17)−0.058 (2)
C120.0567 (15)0.0547 (14)0.116 (2)0.0038 (11)0.0168 (15)−0.0218 (15)
C130.0479 (12)0.0480 (12)0.0686 (15)−0.0024 (11)0.0098 (11)−0.0129 (11)
C140.0947 (18)0.1040 (19)0.0463 (14)0.0072 (17)0.0257 (13)0.0064 (14)
C150.0993 (19)0.0548 (14)0.084 (2)−0.0010 (14)0.0152 (15)0.0136 (13)
C160.0424 (11)0.0557 (12)0.0487 (12)−0.0046 (10)0.0183 (9)−0.0144 (10)
C170.0647 (14)0.0544 (14)0.0845 (18)−0.0083 (12)0.0317 (13)−0.0254 (13)
C180.0756 (19)0.0850 (19)0.116 (2)−0.0164 (16)0.0305 (19)−0.054 (2)
C190.0681 (18)0.157 (3)0.083 (2)−0.012 (2)0.0155 (16)−0.073 (2)
C200.0721 (17)0.138 (3)0.0485 (15)0.0066 (18)0.0157 (12)−0.0192 (17)
C210.0583 (13)0.0787 (16)0.0478 (13)0.0008 (12)0.0228 (10)−0.0080 (11)
C220.137 (3)0.0426 (14)0.138 (3)−0.0030 (16)0.062 (2)−0.0014 (16)
C230.118 (2)0.0892 (19)0.0665 (17)0.0023 (17)0.0486 (16)0.0222 (14)
C240.0433 (11)0.0760 (15)0.0568 (13)0.0023 (11)0.0134 (10)0.0072 (11)
C250.0751 (16)0.0721 (15)0.0663 (16)−0.0134 (13)0.0292 (12)0.0093 (12)
Geometric parameters (Å, °) top
Al1—N11.8783 (15)C13—C151.496 (3)
Al1—C251.943 (2)C14—H14A0.9600
Al1—N21.9453 (15)C14—H14B0.9600
Al1—C241.948 (2)C14—H14C0.9600
N1—C11.365 (2)C15—H15A0.9600
N1—C81.441 (2)C15—H15B0.9600
N2—C71.295 (2)C15—H15C0.9600
N2—C161.441 (2)C16—C171.384 (3)
C1—C21.402 (2)C16—C211.387 (3)
C1—C61.422 (2)C17—C181.384 (3)
C2—C31.360 (3)C17—C221.490 (3)
C2—H20.9300C18—C191.346 (4)
C3—C41.388 (3)C18—H180.9300
C3—H30.9300C19—C201.369 (4)
C4—C51.342 (3)C19—H190.9300
C4—H40.9300C20—C211.371 (3)
C5—C61.410 (2)C20—H200.9300
C5—H50.9300C21—C231.506 (3)
C6—C71.408 (2)C22—H22A0.9600
C7—H70.9300C22—H22B0.9600
C8—C131.387 (3)C22—H22C0.9600
C8—C91.393 (3)C23—H23A0.9600
C9—C101.388 (3)C23—H23B0.9600
C9—C141.488 (3)C23—H23C0.9600
C10—C111.369 (3)C24—H24A0.9600
C10—H100.9300C24—H24B0.9600
C11—C121.364 (4)C24—H24C0.9600
C11—H110.9300C25—H25A0.9600
C12—C131.389 (3)C25—H25B0.9600
C12—H120.9300C25—H25C0.9600
N1—Al1—C25112.62 (8)H14A—C14—H14B109.5
N1—Al1—N293.86 (6)C9—C14—H14C109.5
C25—Al1—N2111.81 (8)H14A—C14—H14C109.5
N1—Al1—C24115.96 (8)H14B—C14—H14C109.5
C25—Al1—C24112.67 (10)C13—C15—H15A109.5
N2—Al1—C24108.36 (8)C13—C15—H15B109.5
C1—N1—C8117.81 (14)H15A—C15—H15B109.5
C1—N1—Al1127.06 (12)C13—C15—H15C109.5
C8—N1—Al1115.10 (10)H15A—C15—H15C109.5
C7—N2—C16117.44 (15)H15B—C15—H15C109.5
C7—N2—Al1122.85 (12)C17—C16—C21122.3 (2)
C16—N2—Al1119.52 (11)C17—C16—N2119.67 (19)
N1—C1—C2122.15 (16)C21—C16—N2118.02 (18)
N1—C1—C6121.20 (15)C18—C17—C16117.0 (2)
C2—C1—C6116.63 (16)C18—C17—C22120.8 (2)
C3—C2—C1121.57 (18)C16—C17—C22122.1 (2)
C3—C2—H2119.2C19—C18—C17121.4 (3)
C1—C2—H2119.2C19—C18—H18119.3
C2—C3—C4121.76 (19)C17—C18—H18119.3
C2—C3—H3119.1C18—C19—C20120.8 (3)
C4—C3—H3119.1C18—C19—H19119.6
C5—C4—C3118.37 (18)C20—C19—H19119.6
C5—C4—H4120.8C19—C20—C21120.5 (3)
C3—C4—H4120.8C19—C20—H20119.7
C4—C5—C6122.28 (19)C21—C20—H20119.7
C4—C5—H5118.9C20—C21—C16117.9 (2)
C6—C5—H5118.9C20—C21—C23120.2 (2)
C7—C6—C5116.65 (17)C16—C21—C23121.9 (2)
C7—C6—C1123.64 (16)C17—C22—H22A109.5
C5—C6—C1119.34 (16)C17—C22—H22B109.5
N2—C7—C6127.61 (17)H22A—C22—H22B109.5
N2—C7—H7116.2C17—C22—H22C109.5
C6—C7—H7116.2H22A—C22—H22C109.5
C13—C8—C9121.40 (18)H22B—C22—H22C109.5
C13—C8—N1118.19 (17)C21—C23—H23A109.5
C9—C8—N1120.39 (17)C21—C23—H23B109.5
C10—C9—C8118.2 (2)H23A—C23—H23B109.5
C10—C9—C14119.6 (2)C21—C23—H23C109.5
C8—C9—C14122.25 (18)H23A—C23—H23C109.5
C11—C10—C9120.5 (2)H23B—C23—H23C109.5
C11—C10—H10119.7Al1—C24—H24A109.5
C9—C10—H10119.7Al1—C24—H24B109.5
C12—C11—C10120.9 (2)H24A—C24—H24B109.5
C12—C11—H11119.5Al1—C24—H24C109.5
C10—C11—H11119.5H24A—C24—H24C109.5
C11—C12—C13120.5 (2)H24B—C24—H24C109.5
C11—C12—H12119.7Al1—C25—H25A109.5
C13—C12—H12119.7Al1—C25—H25B109.5
C8—C13—C12118.4 (2)H25A—C25—H25B109.5
C8—C13—C15121.89 (19)Al1—C25—H25C109.5
C12—C13—C15119.7 (2)H25A—C25—H25C109.5
C9—C14—H14A109.5H25B—C25—H25C109.5
C9—C14—H14B109.5
Table 1
Selected geometric parameters (Å, °) top
Al1—N11.8783 (15)Al1—N21.9453 (15)
Al1—C251.943 (2)Al1—C241.948 (2)
N1—Al1—C25112.62 (8)N1—Al1—C24115.96 (8)
N1—Al1—N293.86 (6)C25—Al1—C24112.67 (10)
C25—Al1—N2111.81 (8)N2—Al1—C24108.36 (8)
Acknowledgements top

The authors thank the National Natural Science Foundation of China for financial support (grant No. 20674024).

references
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