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Acta Cryst. (2011). E67, m469    [ doi:10.1107/S1600536811009469 ]

Bis([eta]3-2-tert-butyl-1-trimethylsilyl-3-phenyl-1-azaallyl)nickel(II)

J. Hao, H. Liu and H.-Y. Yuan

Abstract top

The title compound, [Ni(C15H24NSi)2], is a homoleptic metal-[eta]3-azaallyl centrosymmetric complex containing two azaallyl ligands bound in an [eta]3-manner to an NiII atom located on a center of symmetry. The overall coordination about the NiII atom is square-planar. The C and N atoms of the azaallyl group are sp2-hybridized. The uneven Ni-C and Ni-N distances [2.045 (5)/2.060 (6) and 1.916 (5) Å] are influenced by a steric hindering effect from the nearby benzene ring.

Comment top

Metal-η3-allyl complexes are well known to play an important role in many metal-mediated reactions (Blystone et al., 1989). Lappert and co-workers have prepared a variety of 1-azaallyl complexes containing main group elements and transition metals (Avent et al., 2004; Caro et al., 2001; Hitchcock et al., 2000). Recently, Yuan and co-workers have prepared related Cobalt η^3^-allyl complexes (Yuan et al., 2007). As part of an subsequent investigation of metal-η3-azaallyl complexes, we have prepared the title complex, [Ni(C30H48N2Si2)2], (I),

The title compound is a homoleptic metal-η3-azaallyl centrosymmetric complex containing two azaallyl ligands bound in an η3 manner to a NiII atom located at the center of symmetry, thereby, forming two nonplanar 4-membered rings, N/C8/C7/Ni (Fig. 1). The dihedral angle between the N/C7/Ni and C8/C7/Ni planes is 49.0 (3)°. The C and N atoms of the azaallyl group are sp2– hybridized with the N—C8 bond [1.355 (7) Å] showing double-bond character. The uneven Ni—C7, Ni—C8 and Ni—N distances [2.045 (5), 2.060 (6)Å, and 1.916 (5)Å] are influenced by a steric hindered effect from the nearby benzene ring (C1—C6).

Related literature top

For metal-mediated reactions, see: Blystone (1989). For related 1-azaallyl complexes including some main group elements and transition metals, see: Avent et al. (2004); Caro et al. (2001); Hitchcock et al. (2000). For related cobalt η^3^-allyl complexes, see: Yuan et al. (2007).

Experimental top

All manipulations were carried out under argon or in vacuo using standard Schlenk techniques. The title complex was synthesized according to literature methods (Hitchcock et al., 2000; Avent et al., 2004). To a solution of trimethylsilylmethyltolulithium (6 mmol) in diethyl ether(20 ml), tert-butyl nitrile (6 mmol) was added at ca 273 K and the solution was stirred for 15 min and then for 5 h at room temperature. To this solution, NiCl2(3 mmol) was added at ca 200 K and the suspension was stirred for 15 min and then for 5 h at room temperature. The mixture was filtered and the filtrate was carefully concentrated under a vacuum until yellow crystals of the title compound appeared.

Refinement top

All H atoms were positioned geometrically, with CH = 0.96– 0.98 Å, CH3 = 0.96Å and refined as riding, allowing for free rotation of the methyl groups. The Uiso(H) values were set at 1.18-1.21 Ueq(CH) or 1.5Ueq(CH3).

Computing details top

Data collection: SMART (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. View of the title molecule showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are omitted for clarity. The symmetry operator for i is –X, –Y, –Z.
Bis(η3-2-tert-butyl-1-trimethylsilyl-3-phenyl-1-azaallyl)nickel(II) top
Crystal data top
[Ni(C15H24NSi)2]F(000) = 596
Mr = 551.59Dx = 1.162 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1405 reflections
a = 10.309 (6) Åθ = 2.4–26.7°
b = 9.289 (6) ŵ = 0.71 mm−1
c = 16.521 (9) ÅT = 213 K
β = 94.84 (2)°Block, yellow
V = 1576.4 (16) Å30.30 × 0.30 × 0.20 mm
Z = 2
Data collection top
Siemens SMART CCD area-detector
diffractometer		2776 independent reflections
Radiation source: fine-focus sealed tube2446 reflections with I > 2σ(I)
graphiteRint = 0.061
φ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		h = −12→9
Tmin = 0.815, Tmax = 0.871k = −9→11
7488 measured reflectionsl = −19→19
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)] = 0.096Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.186H-atom parameters constrained
S = 1.36 w = 1/[σ2(Fo2) + (0.0426P)2 + 3.0952P]
where P = (Fo2 + 2Fc2)/3
2776 reflections(Δ/σ)max < 0.001
166 parametersΔρmax = 0.63 e Å−3
0 restraintsΔρmin = −1.22 e Å−3
Crystal data top
[Ni(C15H24NSi)2]V = 1576.4 (16) Å3
Mr = 551.59Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.309 (6) ŵ = 0.71 mm−1
b = 9.289 (6) ÅT = 213 K
c = 16.521 (9) Å0.30 × 0.30 × 0.20 mm
β = 94.84 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		2776 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2009)		2446 reflections with I > 2σ(I)
Tmin = 0.815, Tmax = 0.871Rint = 0.061
7488 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.096H-atom parameters constrained
wR(F2) = 0.186Δρmax = 0.63 e Å−3
S = 1.36Δρmin = −1.22 e Å−3
2776 reflectionsAbsolute structure: ?
166 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
Ni0.50000.50000.00000.0230 (3)
N0.5562 (5)0.5466 (5)0.1104 (3)0.0258 (11)
Si0.60753 (18)0.6959 (2)0.16563 (10)0.0343 (5)
C10.6907 (6)0.2919 (7)0.0403 (4)0.0319 (15)
C20.7162 (8)0.1682 (7)−0.0031 (4)0.0461 (18)
H20.64770.1078−0.02080.055*
C30.8420 (9)0.1330 (10)−0.0205 (5)0.067 (3)
H30.85750.0502−0.04980.080*
C40.9421 (9)0.2215 (11)0.0060 (6)0.071 (3)
H41.02650.1984−0.00520.086*
C50.9199 (7)0.3447 (9)0.0491 (5)0.057 (2)
H50.98870.40470.06700.068*
C60.7934 (7)0.3781 (7)0.0655 (4)0.0404 (17)
H60.77830.46150.09440.048*
C70.5535 (6)0.3120 (6)0.0600 (3)0.0288 (14)
H70.49610.22990.04650.035*
C80.5045 (6)0.4128 (6)0.1139 (3)0.0264 (13)
C90.3895 (6)0.3787 (7)0.1648 (4)0.0354 (15)
C100.3392 (9)0.2272 (9)0.1507 (6)0.079 (3)
H10A0.27480.20660.18780.119*
H10B0.41000.16030.15940.119*
H10C0.30090.21840.09590.119*
C110.4382 (8)0.3936 (10)0.2540 (4)0.064 (2)
H11A0.36790.37540.28720.096*
H11B0.47060.48940.26410.096*
H11C0.50690.32550.26710.096*
C120.2786 (7)0.4838 (9)0.1442 (5)0.063 (2)
H12A0.24720.47280.08810.095*
H12B0.30930.58050.15340.095*
H12C0.20920.46460.17790.095*
C130.7233 (8)0.6372 (9)0.2517 (4)0.059 (2)
H13A0.67650.58870.29140.088*
H13B0.76690.71980.27600.088*
H13C0.78640.57280.23200.088*
C140.4802 (8)0.8102 (8)0.2082 (5)0.063 (2)
H14A0.41870.84180.16500.094*
H14B0.52060.89250.23500.094*
H14C0.43580.75510.24650.094*
C150.6989 (9)0.8097 (9)0.0976 (5)0.066 (3)
H15A0.76160.75170.07270.099*
H15B0.74300.88520.12860.099*
H15C0.63940.85120.05620.099*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.0255 (6)0.0245 (6)0.0189 (5)−0.0018 (5)0.0021 (4)0.0027 (5)
N0.029 (3)0.027 (3)0.022 (2)0.007 (2)0.006 (2)0.003 (2)
Si0.0386 (11)0.0359 (10)0.0281 (9)−0.0032 (8)0.0005 (8)−0.0048 (8)
C10.035 (4)0.033 (4)0.028 (3)0.007 (3)0.003 (3)0.014 (3)
C20.057 (5)0.040 (4)0.042 (4)0.011 (4)0.008 (4)0.007 (3)
C30.074 (7)0.058 (6)0.072 (6)0.030 (5)0.025 (5)0.008 (5)
C40.048 (6)0.082 (7)0.088 (7)0.032 (5)0.028 (5)0.027 (6)
C50.035 (5)0.074 (6)0.061 (5)0.007 (4)0.003 (4)0.019 (4)
C60.038 (4)0.046 (4)0.038 (4)0.001 (3)0.006 (3)0.008 (3)
C70.041 (4)0.020 (3)0.025 (3)−0.003 (3)−0.001 (3)0.004 (3)
C80.022 (3)0.030 (3)0.027 (3)−0.008 (3)−0.002 (3)0.013 (3)
C90.033 (4)0.043 (4)0.031 (3)−0.007 (3)0.010 (3)0.002 (3)
C100.090 (7)0.067 (6)0.088 (7)−0.036 (5)0.054 (6)−0.007 (5)
C110.058 (5)0.099 (7)0.037 (4)0.002 (5)0.016 (4)0.013 (4)
C120.043 (5)0.079 (6)0.070 (5)0.003 (4)0.022 (4)0.028 (5)
C130.061 (6)0.067 (5)0.046 (4)−0.006 (4)−0.012 (4)−0.005 (4)
C140.067 (6)0.054 (5)0.066 (5)0.012 (4)−0.001 (4)−0.022 (4)
C150.089 (7)0.062 (5)0.048 (5)−0.043 (5)0.007 (4)−0.001 (4)
Geometric parameters (Å, °) top
Ni—N1.916 (5)C7—H70.9800
Ni—Ni1.916 (5)C8—C91.544 (8)
Ni—C82.045 (5)C9—C101.511 (10)
Ni—C8i2.045 (5)C9—C121.521 (10)
Ni—C7i2.060 (6)C9—C111.523 (9)
Ni—C72.060 (6)C10—H10A0.9600
N—C81.355 (7)C10—H10B0.9600
N—Si1.720 (5)C10—H10C0.9600
Si—C151.857 (7)C11—H11A0.9600
Si—C131.860 (8)C11—H11B0.9600
Si—C141.871 (7)C11—H11C0.9600
C1—C61.365 (9)C12—H12A0.9600
C1—C21.390 (9)C12—H12B0.9600
C1—C71.490 (8)C12—H12C0.9600
C2—C31.390 (10)C13—H13A0.9600
C2—H20.9300C13—H13B0.9600
C3—C41.362 (12)C13—H13C0.9600
C3—H30.9300C14—H14A0.9600
C4—C51.377 (11)C14—H14B0.9600
C4—H40.9300C14—H14C0.9600
C5—C61.389 (9)C15—H15A0.9600
C5—H50.9300C15—H15B0.9600
C6—H60.9300C15—H15C0.9600
C7—C81.414 (8)
N—Ni—Ni180.0N—C8—C7114.7 (5)
N—Ni—C839.8 (2)N—C8—C9122.3 (5)
Ni—Ni—C8140.2 (2)C7—C8—C9122.6 (5)
N—Ni—C8i140.2 (2)N—C8—Ni64.9 (3)
Ni—Ni—C8i39.8 (2)C7—C8—Ni70.4 (3)
C8—Ni—C8i180.0C9—C8—Ni128.6 (4)
N—Ni—C7i108.3 (2)C10—C9—C12108.8 (7)
Ni—Ni—C7i71.7 (2)C10—C9—C11108.4 (6)
C8—Ni—C7i139.7 (2)C12—C9—C11109.8 (6)
C8i—Ni—C7i40.3 (2)C10—C9—C8112.1 (5)
N—Ni—C771.7 (2)C12—C9—C8110.1 (5)
Ni—Ni—C7108.3 (2)C11—C9—C8107.7 (5)
C8—Ni—C740.3 (2)C9—C10—H10A109.5
C8i—Ni—C7139.7 (2)C9—C10—H10B109.5
C7i—Ni—C7180.0H10A—C10—H10B109.5
C8—N—Si145.2 (4)C9—C10—H10C109.5
C8—N—Ni75.2 (3)H10A—C10—H10C109.5
Si—N—Ni137.9 (3)H10B—C10—H10C109.5
N—Si—C15106.7 (3)C9—C11—H11A109.5
N—Si—C13108.5 (3)C9—C11—H11B109.5
C15—Si—C13107.7 (4)H11A—C11—H11B109.5
N—Si—C14117.6 (3)C9—C11—H11C109.5
C15—Si—C14108.2 (4)H11A—C11—H11C109.5
C13—Si—C14107.7 (4)H11B—C11—H11C109.5
C6—C1—C2117.8 (6)C9—C12—H12A109.5
C6—C1—C7125.8 (6)C9—C12—H12B109.5
C2—C1—C7116.2 (6)H12A—C12—H12B109.5
C1—C2—C3121.4 (8)C9—C12—H12C109.5
C1—C2—H2119.3H12A—C12—H12C109.5
C3—C2—H2119.3H12B—C12—H12C109.5
C4—C3—C2119.1 (8)Si—C13—H13A109.5
C4—C3—H3120.5Si—C13—H13B109.5
C2—C3—H3120.5H13A—C13—H13B109.5
C3—C4—C5120.9 (8)Si—C13—H13C109.5
C3—C4—H4119.6H13A—C13—H13C109.5
C5—C4—H4119.6H13B—C13—H13C109.5
C4—C5—C6119.1 (8)Si—C14—H14A109.5
C4—C5—H5120.5Si—C14—H14B109.5
C6—C5—H5120.5H14A—C14—H14B109.5
C1—C6—C5121.8 (7)Si—C14—H14C109.5
C1—C6—H6119.1H14A—C14—H14C109.5
C5—C6—H6119.1H14B—C14—H14C109.5
C8—C7—C1128.1 (5)Si—C15—H15A109.5
C8—C7—Ni69.3 (3)Si—C15—H15B109.5
C1—C7—Ni102.8 (4)H15A—C15—H15B109.5
C8—C7—H7114.7Si—C15—H15C109.5
C1—C7—H7114.7H15A—C15—H15C109.5
Ni—C7—H7114.7H15B—C15—H15C109.5
Symmetry codes: (i) −x+1, −y+1, −z.
Acknowledgements top

We thank the Natural Science Foundation of China (grant No. 20772074).

references
References top

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