Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103003172/fr1410sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103003172/fr1410Isup2.hkl |
CCDC reference: 211722
All experiments were conducted under an argon atmosphere. The solvents were dried and distilled prior to use. IsodiCpHSiMe2NHtBu and Zr(NMe2)4 (Diamond et al., 1995; Gentil et al., 2000) were prepared according to the published methods. IsodiCpHSiMe2NHtBu (3.74 mmol, 977 mg) was added to Zr(NMe2)4 (1.00 g, 3.74 mmol) without any solvent. The reaction mixture was heated at 423 K for 12 h. Me2NH was removed from the flask by periodic evacuation. The resulting product was collected by sublimation at 433 K in a yield of 86%. Dissolution of the solid in a toluene/pentane (1:5) solution and cooling at 243 K for 2 d afforded colourless crystals of (I) suitable for X-ray analysis.
The tert-butyl group is disordered over two orientations. The occupancy factor for the major orientation (atom labels C14A, C15A and C16A) refined to 0.821 (6) and this set of atoms was refined anisotropically. The minor orientation (atom labels C14B, C15B, C16B) was kept isotropic with an occupancy factor of 0.179 (6). A SADI restraint (SHELXL97; Sheldrick, 1997) was used for the minor component to restrain the three C—C bonds to be equal. Methyl H atoms were added at calculated positions using a riding model, with C—H distances of 0.98 Å Is this added text OK? and Uiso(H) = 1.5Ueq(C). For each methyl group, the torsion angle which defines the orientation about the Si—C, N—C, or C—C bond was refined. The remaining H atoms were included in the model at calculated positions using a riding model, with C—H distances in the range 0.95–1.00 Å Is this added text OK? and Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 1999); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: PLATON (Spek, 1990).
[Zr(C16H25NSi)(C2H6N)2] | F(000) = 1856 |
Mr = 438.84 | Dx = 1.272 Mg m−3 |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 4545 reflections |
a = 10.593 (1) Å | θ = 2.0–25.0° |
b = 15.134 (2) Å | µ = 0.54 mm−1 |
c = 28.592 (3) Å | T = 150 K |
V = 4583.7 (9) Å3 | Rectangular block, colourless |
Z = 8 | 0.35 × 0.31 × 0.19 mm |
Nonius Kappa CCD aarea-detector diffractometer | 4038 independent reflections |
Radiation source: fine-focus sealed tube | 3443 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | h = −12→12 |
Tmin = 0.849, Tmax = 0.902 | k = −18→18 |
41422 measured reflections | l = −34→34 |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0361P)2 + 6.0948P] where P = (Fo2 + 2Fc2)/3 |
4038 reflections | (Δ/σ)max = 0.010 |
251 parameters | Δρmax = 0.80 e Å−3 |
3 restraints | Δρmin = −0.41 e Å−3 |
[Zr(C16H25NSi)(C2H6N)2] | V = 4583.7 (9) Å3 |
Mr = 438.84 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 10.593 (1) Å | µ = 0.54 mm−1 |
b = 15.134 (2) Å | T = 150 K |
c = 28.592 (3) Å | 0.35 × 0.31 × 0.19 mm |
Nonius Kappa CCD aarea-detector diffractometer | 4038 independent reflections |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) | 3443 reflections with I > 2σ(I) |
Tmin = 0.849, Tmax = 0.902 | Rint = 0.038 |
41422 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | 3 restraints |
wR(F2) = 0.080 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.80 e Å−3 |
4038 reflections | Δρmin = −0.41 e Å−3 |
251 parameters |
Experimental. All work was done at 150 K using an Oxford Cryosystems Cryostream Cooler. An octant of data was measured with a redundancy factor of 4, which means that 90% of the data was measured at least 4 times. A combination of phi and omega scans with a frame width of 1.0° was used for data collection. Data integration was done with DENZO (Otwinowski & Minor, 1997). 1H and 13C NMR spectra were recorded with a Bruker DRX500 spectrometer. 1H NMR (C6D6, δ, p.p.m.): 5.86 (s, 2H, peripheral), 3.23 (br s, 2H, bridgehead), 3.02 (s, 6H, N(CH3)2), 1.75 (br m, 3H, syn-methano and exo-ethano bridge), 1.48 (d, 1H, 2JHH = 8.93 Hz, anti-methano bridge), 1.45 (s, 9H, NC(CH3)3), 1.20 (d, 2H, 2JHH = 7.24 Hz, endo-ethano bridge), 0.67 (s, 6H, SiCH3); 13C {1H} NMR (C6D6, δ, p.p.m.): 143.6 (quaternary), 108.8 (peripheral), 106.9 (central), 56.3 (NC(CH3)3), 50.7 (methano bridge), 44.7 [N(CH3)2], 40.5 (bridgehead), 35.1 [NC(CH3)3], 29.3 (ethano bridge), 21.9 (CH3), 3.0 (SiCH3). |
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 | Occ. (<1) | |
Zr | 0.52498 (2) | 0.619386 (15) | 0.620355 (8) | 0.01794 (9) | |
Si | 0.25163 (6) | 0.56073 (4) | 0.62692 (2) | 0.01937 (16) | |
N1 | 0.39431 (19) | 0.53359 (13) | 0.65236 (7) | 0.0211 (4) | |
N2 | 0.6881 (2) | 0.55190 (16) | 0.60438 (8) | 0.0320 (5) | |
N3 | 0.5715 (3) | 0.70843 (15) | 0.67145 (9) | 0.0406 (6) | |
C1 | 0.4905 (2) | 0.66138 (16) | 0.53311 (8) | 0.0194 (5) | |
C2 | 0.4012 (2) | 0.59733 (15) | 0.54545 (8) | 0.0193 (5) | |
H2 | 0.3952 | 0.5396 | 0.5326 | 0.023* | |
C3 | 0.3203 (2) | 0.63358 (15) | 0.58090 (8) | 0.0178 (5) | |
C4 | 0.3603 (2) | 0.72356 (15) | 0.58790 (8) | 0.0192 (5) | |
H4 | 0.3218 | 0.7653 | 0.6082 | 0.023* | |
C5 | 0.4666 (2) | 0.73885 (15) | 0.55939 (8) | 0.0193 (5) | |
C6 | 0.5513 (2) | 0.81018 (17) | 0.54014 (9) | 0.0254 (6) | |
H6 | 0.5685 | 0.8614 | 0.5613 | 0.030* | |
C7 | 0.4975 (3) | 0.83286 (18) | 0.49097 (10) | 0.0311 (7) | |
H7A | 0.4059 | 0.8455 | 0.4926 | 0.037* | |
H7B | 0.5413 | 0.8846 | 0.4773 | 0.037* | |
C8 | 0.5235 (3) | 0.74808 (19) | 0.46191 (9) | 0.0315 (6) | |
H8A | 0.5791 | 0.7610 | 0.4349 | 0.038* | |
H8B | 0.4438 | 0.7218 | 0.4503 | 0.038* | |
C9 | 0.5899 (2) | 0.68537 (17) | 0.49730 (9) | 0.0252 (6) | |
H9 | 0.6387 | 0.6351 | 0.4836 | 0.030* | |
C10 | 0.6671 (2) | 0.75396 (17) | 0.52568 (9) | 0.0269 (6) | |
H10A | 0.7110 | 0.7274 | 0.5528 | 0.032* | |
H10B | 0.7277 | 0.7872 | 0.5061 | 0.032* | |
C11 | 0.1415 (3) | 0.62432 (18) | 0.66512 (10) | 0.0327 (6) | |
H11A | 0.1039 | 0.5846 | 0.6883 | 0.049* | |
H11B | 0.0745 | 0.6505 | 0.6459 | 0.049* | |
H11C | 0.1881 | 0.6713 | 0.6812 | 0.049* | |
C12 | 0.1610 (3) | 0.46851 (17) | 0.59900 (10) | 0.0305 (6) | |
H12A | 0.0924 | 0.4931 | 0.5800 | 0.046* | |
H12B | 0.1255 | 0.4303 | 0.6234 | 0.046* | |
H12C | 0.2176 | 0.4339 | 0.5790 | 0.046* | |
C13 | 0.4185 (3) | 0.46247 (18) | 0.68666 (10) | 0.0345 (7) | |
C14A | 0.5416 (4) | 0.4785 (3) | 0.71187 (14) | 0.0490 (13) | 0.821 (6) |
H14A | 0.6099 | 0.4843 | 0.6890 | 0.073* | 0.821 (6) |
H14B | 0.5594 | 0.4287 | 0.7328 | 0.073* | 0.821 (6) |
H14C | 0.5354 | 0.5330 | 0.7302 | 0.073* | 0.821 (6) |
C15A | 0.4411 (5) | 0.3758 (2) | 0.65758 (16) | 0.0510 (13) | 0.821 (6) |
H15A | 0.5109 | 0.3851 | 0.6356 | 0.076* | 0.821 (6) |
H15B | 0.3643 | 0.3609 | 0.6402 | 0.076* | 0.821 (6) |
H15C | 0.4624 | 0.3272 | 0.6788 | 0.076* | 0.821 (6) |
C16A | 0.3117 (4) | 0.4483 (4) | 0.71881 (17) | 0.0646 (17) | 0.821 (6) |
H16A | 0.3312 | 0.3991 | 0.7399 | 0.097* | 0.821 (6) |
H16B | 0.2357 | 0.4343 | 0.7007 | 0.097* | 0.821 (6) |
H16C | 0.2973 | 0.5020 | 0.7372 | 0.097* | 0.821 (6) |
C14B | 0.402 (2) | 0.5159 (13) | 0.7350 (6) | 0.059 (6)* | 0.179 (6) |
H14D | 0.3264 | 0.5532 | 0.7331 | 0.089* | 0.179 (6) |
H14E | 0.4762 | 0.5530 | 0.7403 | 0.089* | 0.179 (6) |
H14F | 0.3927 | 0.4739 | 0.7608 | 0.089* | 0.179 (6) |
C15B | 0.5513 (17) | 0.4164 (17) | 0.6908 (10) | 0.077 (8)* | 0.179 (6) |
H15D | 0.6180 | 0.4610 | 0.6882 | 0.116* | 0.179 (6) |
H15E | 0.5608 | 0.3729 | 0.6657 | 0.116* | 0.179 (6) |
H15F | 0.5578 | 0.3866 | 0.7212 | 0.116* | 0.179 (6) |
C16B | 0.3047 (16) | 0.3961 (12) | 0.6934 (7) | 0.047 (5)* | 0.179 (6) |
H16D | 0.3036 | 0.3536 | 0.6675 | 0.071* | 0.179 (6) |
H16E | 0.2251 | 0.4291 | 0.6938 | 0.071* | 0.179 (6) |
H16F | 0.3148 | 0.3643 | 0.7230 | 0.071* | 0.179 (6) |
C17 | 0.6999 (3) | 0.4869 (2) | 0.56820 (13) | 0.0598 (10) | |
H17A | 0.6200 | 0.4823 | 0.5511 | 0.090* | |
H17B | 0.7206 | 0.4296 | 0.5822 | 0.090* | |
H17C | 0.7672 | 0.5044 | 0.5466 | 0.090* | |
C18 | 0.8094 (3) | 0.5652 (3) | 0.62702 (14) | 0.0591 (10) | |
H18A | 0.8011 | 0.6106 | 0.6513 | 0.089* | |
H18B | 0.8716 | 0.5843 | 0.6038 | 0.089* | |
H18C | 0.8372 | 0.5097 | 0.6413 | 0.089* | |
C19 | 0.4956 (4) | 0.7295 (3) | 0.71455 (13) | 0.0662 (11) | |
H19A | 0.4311 | 0.6840 | 0.7192 | 0.099* | |
H19B | 0.4547 | 0.7872 | 0.7107 | 0.099* | |
H19C | 0.5516 | 0.7312 | 0.7418 | 0.099* | |
C20 | 0.6559 (5) | 0.7791 (3) | 0.66411 (14) | 0.0848 (16) | |
H20A | 0.7010 | 0.7702 | 0.6346 | 0.127* | |
H20B | 0.7167 | 0.7816 | 0.6899 | 0.127* | |
H20C | 0.6086 | 0.8347 | 0.6628 | 0.127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Zr | 0.01658 (14) | 0.01852 (14) | 0.01872 (14) | −0.00120 (9) | −0.00261 (9) | 0.00062 (9) |
Si | 0.0180 (3) | 0.0171 (3) | 0.0230 (3) | −0.0016 (3) | 0.0015 (3) | 0.0024 (3) |
N1 | 0.0229 (11) | 0.0210 (10) | 0.0195 (11) | −0.0002 (9) | −0.0018 (9) | 0.0039 (8) |
N2 | 0.0217 (12) | 0.0413 (14) | 0.0329 (12) | 0.0086 (10) | 0.0004 (10) | 0.0044 (11) |
N3 | 0.0570 (16) | 0.0265 (12) | 0.0382 (14) | −0.0043 (12) | −0.0197 (13) | −0.0057 (11) |
C1 | 0.0192 (13) | 0.0216 (13) | 0.0174 (12) | 0.0026 (10) | −0.0011 (10) | 0.0017 (10) |
C2 | 0.0222 (13) | 0.0186 (12) | 0.0169 (12) | 0.0003 (10) | −0.0048 (10) | −0.0007 (9) |
C3 | 0.0150 (12) | 0.0184 (12) | 0.0199 (12) | −0.0002 (9) | −0.0032 (10) | 0.0028 (9) |
C4 | 0.0175 (12) | 0.0170 (12) | 0.0233 (13) | 0.0027 (10) | 0.0007 (10) | 0.0017 (10) |
C5 | 0.0174 (12) | 0.0184 (12) | 0.0219 (12) | −0.0004 (10) | −0.0020 (10) | 0.0038 (10) |
C6 | 0.0214 (14) | 0.0224 (13) | 0.0324 (15) | −0.0043 (10) | 0.0021 (11) | 0.0043 (11) |
C7 | 0.0257 (15) | 0.0312 (15) | 0.0364 (16) | −0.0033 (11) | 0.0016 (12) | 0.0167 (13) |
C8 | 0.0278 (15) | 0.0429 (16) | 0.0237 (14) | −0.0047 (13) | 0.0047 (11) | 0.0100 (12) |
C9 | 0.0218 (14) | 0.0301 (14) | 0.0237 (13) | 0.0009 (11) | 0.0056 (11) | 0.0007 (11) |
C10 | 0.0185 (13) | 0.0322 (14) | 0.0300 (14) | −0.0032 (11) | 0.0028 (11) | 0.0072 (12) |
C11 | 0.0286 (15) | 0.0322 (15) | 0.0372 (16) | 0.0029 (12) | 0.0101 (13) | 0.0045 (12) |
C12 | 0.0273 (15) | 0.0251 (14) | 0.0391 (16) | −0.0057 (11) | −0.0044 (12) | 0.0046 (12) |
C13 | 0.0350 (16) | 0.0318 (15) | 0.0367 (16) | −0.0028 (13) | −0.0091 (13) | 0.0172 (12) |
C14A | 0.059 (3) | 0.045 (2) | 0.043 (2) | −0.003 (2) | −0.026 (2) | 0.0227 (19) |
C15A | 0.070 (3) | 0.0232 (19) | 0.060 (3) | 0.0045 (19) | −0.020 (2) | 0.0098 (17) |
C16A | 0.056 (3) | 0.080 (4) | 0.057 (3) | 0.014 (3) | 0.016 (2) | 0.048 (3) |
C17 | 0.051 (2) | 0.071 (2) | 0.057 (2) | 0.0331 (19) | −0.0021 (18) | −0.0169 (19) |
C18 | 0.0292 (17) | 0.064 (2) | 0.084 (3) | 0.0085 (17) | −0.0139 (18) | 0.009 (2) |
C19 | 0.091 (3) | 0.058 (2) | 0.049 (2) | −0.001 (2) | −0.003 (2) | −0.0160 (19) |
C20 | 0.137 (4) | 0.071 (3) | 0.046 (2) | −0.059 (3) | −0.005 (2) | −0.011 (2) |
Zr—N3 | 2.048 (2) | C11—H11B | 0.98 |
Zr—N2 | 2.059 (2) | C11—H11C | 0.98 |
Zr—N1 | 2.107 (2) | C12—H12A | 0.98 |
Zr—C3 | 2.454 (2) | C12—H12B | 0.98 |
Zr—C4 | 2.528 (2) | C12—H12C | 0.98 |
Zr—C2 | 2.533 (2) | C13—C16A | 1.473 (5) |
Zr—C5 | 2.587 (2) | C13—C14A | 1.509 (5) |
Zr—C1 | 2.600 (2) | C13—C15A | 1.572 (5) |
Zr—Si | 3.0343 (7) | C13—C15B | 1.575 (14) |
Si—N1 | 1.727 (2) | C13—C16B | 1.582 (13) |
Si—C3 | 1.864 (2) | C13—C14B | 1.610 (13) |
Si—C11 | 1.866 (3) | C14A—H14A | 0.98 |
Si—C12 | 1.873 (3) | C14A—H14B | 0.98 |
N1—C13 | 1.478 (3) | C14A—H14C | 0.98 |
N2—C17 | 1.433 (4) | C15A—H15A | 0.98 |
N2—C18 | 1.452 (4) | C15A—H15B | 0.98 |
N3—C20 | 1.410 (4) | C15A—H15C | 0.98 |
N3—C19 | 1.506 (5) | C16A—H16A | 0.98 |
C1—C2 | 1.399 (3) | C16A—H16B | 0.98 |
C1—C5 | 1.415 (3) | C16A—H16C | 0.98 |
C1—C9 | 1.513 (3) | C14B—H14D | 0.98 |
C2—C3 | 1.437 (3) | C14B—H14E | 0.98 |
C2—H2 | 0.95 | C14B—H14F | 0.98 |
C3—C4 | 1.440 (3) | C15B—H15D | 0.98 |
C4—C5 | 1.409 (3) | C15B—H15E | 0.98 |
C4—H4 | 0.95 | C15B—H15F | 0.98 |
C5—C6 | 1.508 (3) | C16B—H16D | 0.98 |
C6—C10 | 1.549 (4) | C16B—H16E | 0.98 |
C6—C7 | 1.555 (4) | C16B—H16F | 0.98 |
C6—H6 | 1.00 | C17—H17A | 0.98 |
C7—C8 | 1.553 (4) | C17—H17B | 0.98 |
C7—H7A | 0.99 | C17—H17C | 0.98 |
C7—H7B | 0.99 | C18—H18A | 0.98 |
C8—C9 | 1.555 (4) | C18—H18B | 0.98 |
C8—H8A | 0.99 | C18—H18C | 0.98 |
C8—H8B | 0.99 | C19—H19A | 0.98 |
C9—C10 | 1.550 (4) | C19—H19B | 0.98 |
C9—H9 | 1.00 | C19—H19C | 0.98 |
C10—H10A | 0.99 | C20—H20A | 0.98 |
C10—H10B | 0.99 | C20—H20B | 0.98 |
C11—H11A | 0.98 | C20—H20C | 0.98 |
N3—Zr—N2 | 106.42 (10) | C9—C8—H8B | 111.0 |
N3—Zr—N1 | 104.71 (9) | H8A—C8—H8B | 109.0 |
N2—Zr—N1 | 110.00 (9) | C1—C9—C10 | 99.99 (19) |
N3—Zr—C3 | 118.89 (9) | C1—C9—C8 | 105.8 (2) |
N2—Zr—C3 | 133.10 (9) | C10—C9—C8 | 99.8 (2) |
N1—Zr—C3 | 70.92 (8) | C1—C9—H9 | 116.3 |
N3—Zr—C4 | 91.01 (9) | C10—C9—H9 | 116.3 |
N2—Zr—C4 | 143.83 (8) | C8—C9—H9 | 116.3 |
N1—Zr—C4 | 95.20 (8) | C6—C10—C9 | 95.18 (19) |
C3—Zr—C4 | 33.57 (7) | C6—C10—H10A | 112.7 |
N3—Zr—C2 | 144.54 (9) | C9—C10—H10A | 112.7 |
N2—Zr—C2 | 100.45 (8) | C6—C10—H10B | 112.7 |
N1—Zr—C2 | 86.91 (8) | C9—C10—H10B | 112.7 |
C3—Zr—C2 | 33.44 (8) | H10A—C10—H10B | 110.2 |
C4—Zr—C2 | 54.18 (8) | Si—C11—H11A | 109.5 |
N3—Zr—C5 | 94.49 (9) | Si—C11—H11B | 109.5 |
N2—Zr—C5 | 113.46 (8) | H11A—C11—H11B | 109.5 |
N1—Zr—C5 | 124.50 (7) | Si—C11—H11C | 109.5 |
C3—Zr—C5 | 54.38 (7) | H11A—C11—H11C | 109.5 |
C4—Zr—C5 | 31.95 (7) | H11B—C11—H11C | 109.5 |
C2—Zr—C5 | 53.02 (7) | Si—C12—H12A | 109.5 |
N3—Zr—C1 | 123.87 (9) | Si—C12—H12B | 109.5 |
N2—Zr—C1 | 91.51 (8) | H12A—C12—H12B | 109.5 |
N1—Zr—C1 | 118.36 (8) | Si—C12—H12C | 109.5 |
C3—Zr—C1 | 54.08 (8) | H12A—C12—H12C | 109.5 |
C4—Zr—C1 | 53.01 (8) | H12B—C12—H12C | 109.5 |
C2—Zr—C1 | 31.60 (8) | N1—C13—C16A | 112.8 (3) |
C5—Zr—C1 | 31.67 (7) | N1—C13—C14A | 110.4 (2) |
N1—Si—C3 | 95.55 (10) | C16A—C13—C14A | 112.9 (3) |
N1—Si—C11 | 115.06 (12) | N1—C13—C15A | 106.5 (2) |
C3—Si—C11 | 110.61 (11) | C16A—C13—C15A | 109.0 (3) |
N1—Si—C12 | 116.81 (11) | C14A—C13—C15A | 104.8 (3) |
C3—Si—C12 | 109.87 (12) | N1—C13—C15B | 121.9 (10) |
C11—Si—C12 | 108.26 (13) | N1—C13—C16B | 114.3 (7) |
C13—N1—Si | 127.19 (17) | C15B—C13—C16B | 113.0 (13) |
C13—N1—Zr | 128.52 (16) | N1—C13—C14B | 100.6 (8) |
Si—N1—Zr | 104.21 (9) | C15B—C13—C14B | 104.8 (13) |
C17—N2—C18 | 109.9 (3) | C16B—C13—C14B | 97.5 (11) |
C17—N2—Zr | 125.0 (2) | C13—C14A—H14A | 109.5 |
C18—N2—Zr | 125.1 (2) | C13—C14A—H14B | 109.5 |
C20—N3—C19 | 107.4 (3) | C13—C14A—H14C | 109.5 |
C20—N3—Zr | 123.1 (2) | C13—C15A—H15A | 109.5 |
C19—N3—Zr | 126.5 (2) | C13—C15A—H15B | 109.5 |
C2—C1—C5 | 108.6 (2) | C13—C15A—H15C | 109.5 |
C2—C1—C9 | 143.8 (2) | C13—C16A—H16A | 109.5 |
C5—C1—C9 | 106.6 (2) | C13—C16A—H16B | 109.5 |
C2—C1—Zr | 71.56 (13) | C13—C16A—H16C | 109.5 |
C5—C1—Zr | 73.64 (13) | C13—C14B—H14D | 109.5 |
C9—C1—Zr | 127.59 (16) | C13—C14B—H14E | 109.5 |
C1—C2—C3 | 108.5 (2) | H14D—C14B—H14E | 109.5 |
C1—C2—Zr | 76.84 (14) | C13—C14B—H14F | 109.5 |
C3—C2—Zr | 70.24 (13) | H14D—C14B—H14F | 109.5 |
C1—C2—H2 | 125.8 | H14E—C14B—H14F | 109.5 |
C3—C2—H2 | 125.8 | C13—C15B—H15D | 109.5 |
Zr—C2—H2 | 118.9 | C13—C15B—H15E | 109.5 |
C2—C3—C4 | 106.5 (2) | H15D—C15B—H15E | 109.5 |
C2—C3—Si | 120.33 (17) | C13—C15B—H15F | 109.5 |
C4—C3—Si | 125.17 (18) | H15D—C15B—H15F | 109.5 |
C2—C3—Zr | 76.31 (13) | H15E—C15B—H15F | 109.5 |
C4—C3—Zr | 76.03 (13) | C13—C16B—H16D | 109.5 |
Si—C3—Zr | 88.19 (9) | C13—C16B—H16E | 109.5 |
C5—C4—C3 | 108.1 (2) | H16D—C16B—H16E | 109.5 |
C5—C4—Zr | 76.33 (13) | C13—C16B—H16F | 109.5 |
C3—C4—Zr | 70.40 (13) | H16D—C16B—H16F | 109.5 |
C5—C4—H4 | 126.0 | H16E—C16B—H16F | 109.5 |
C3—C4—H4 | 126.0 | N2—C17—H17A | 109.5 |
Zr—C4—H4 | 119.1 | N2—C17—H17B | 109.5 |
C4—C5—C1 | 108.3 (2) | H17A—C17—H17B | 109.5 |
C4—C5—C6 | 143.5 (2) | N2—C17—H17C | 109.5 |
C1—C5—C6 | 107.0 (2) | H17A—C17—H17C | 109.5 |
C4—C5—Zr | 71.71 (13) | H17B—C17—H17C | 109.5 |
C1—C5—Zr | 74.69 (13) | N2—C18—H18A | 109.5 |
C6—C5—Zr | 127.16 (16) | N2—C18—H18B | 109.5 |
C5—C6—C10 | 100.10 (19) | H18A—C18—H18B | 109.5 |
C5—C6—C7 | 105.6 (2) | N2—C18—H18C | 109.5 |
C10—C6—C7 | 99.8 (2) | H18A—C18—H18C | 109.5 |
C5—C6—H6 | 116.3 | H18B—C18—H18C | 109.5 |
C10—C6—H6 | 116.3 | N3—C19—H19A | 109.5 |
C7—C6—H6 | 116.3 | N3—C19—H19B | 109.5 |
C8—C7—C6 | 103.7 (2) | H19A—C19—H19B | 109.5 |
C8—C7—H7A | 111.0 | N3—C19—H19C | 109.5 |
C6—C7—H7A | 111.0 | H19A—C19—H19C | 109.5 |
C8—C7—H7B | 111.0 | H19B—C19—H19C | 109.5 |
C6—C7—H7B | 111.0 | N3—C20—H20A | 109.5 |
H7A—C7—H7B | 109.0 | N3—C20—H20B | 109.5 |
C7—C8—C9 | 103.7 (2) | H20A—C20—H20B | 109.5 |
C7—C8—H8A | 111.0 | N3—C20—H20C | 109.5 |
C9—C8—H8A | 111.0 | H20A—C20—H20C | 109.5 |
C7—C8—H8B | 111.0 | H20B—C20—H20C | 109.5 |
N3—Zr—Si—N1 | −83.08 (12) | C1—C2—C3—C4 | 2.7 (3) |
N2—Zr—Si—N1 | 58.12 (13) | Zr—C2—C3—C4 | 70.67 (15) |
C3—Zr—Si—N1 | 167.96 (14) | C1—C2—C3—Si | −147.60 (17) |
C4—Zr—Si—N1 | −162.34 (12) | Zr—C2—C3—Si | −79.62 (15) |
C2—Zr—Si—N1 | 135.71 (12) | C1—C2—C3—Zr | −67.98 (17) |
C5—Zr—Si—N1 | −178.36 (11) | N1—Si—C3—C2 | 64.9 (2) |
C1—Zr—Si—N1 | 149.99 (11) | C11—Si—C3—C2 | −175.71 (19) |
N3—Zr—Si—C3 | 108.96 (12) | C12—Si—C3—C2 | −56.3 (2) |
N2—Zr—Si—C3 | −109.84 (12) | Zr—Si—C3—C2 | 72.98 (18) |
N1—Zr—Si—C3 | −167.96 (14) | N1—Si—C3—C4 | −79.6 (2) |
C4—Zr—Si—C3 | 29.70 (11) | C11—Si—C3—C4 | 39.8 (2) |
C2—Zr—Si—C3 | −32.25 (11) | C12—Si—C3—C4 | 159.3 (2) |
C5—Zr—Si—C3 | 13.68 (10) | Zr—Si—C3—C4 | −71.47 (19) |
C1—Zr—Si—C3 | −17.97 (10) | N1—Si—C3—Zr | −8.11 (9) |
N3—Zr—Si—C11 | 13.44 (13) | C11—Si—C3—Zr | 111.31 (12) |
N2—Zr—Si—C11 | 154.64 (13) | C12—Si—C3—Zr | −129.23 (10) |
N1—Zr—Si—C11 | 96.53 (14) | N3—Zr—C3—C2 | 148.49 (14) |
C3—Zr—Si—C11 | −95.51 (14) | N2—Zr—C3—C2 | −14.95 (18) |
C4—Zr—Si—C11 | −65.81 (12) | N1—Zr—C3—C2 | −114.85 (14) |
C2—Zr—Si—C11 | −127.76 (12) | C4—Zr—C3—C2 | 111.16 (19) |
C5—Zr—Si—C11 | −81.84 (12) | C5—Zr—C3—C2 | 75.06 (14) |
C1—Zr—Si—C11 | −113.49 (12) | C1—Zr—C3—C2 | 35.76 (13) |
N3—Zr—Si—C12 | −166.97 (14) | Si—Zr—C3—C2 | −121.85 (16) |
N2—Zr—Si—C12 | −25.77 (15) | N3—Zr—C3—C4 | 37.33 (17) |
N1—Zr—Si—C12 | −83.88 (16) | N2—Zr—C3—C4 | −126.11 (15) |
C3—Zr—Si—C12 | 84.08 (15) | N1—Zr—C3—C4 | 133.99 (15) |
C4—Zr—Si—C12 | 113.77 (14) | C2—Zr—C3—C4 | −111.16 (19) |
C2—Zr—Si—C12 | 51.82 (13) | C5—Zr—C3—C4 | −36.10 (13) |
C5—Zr—Si—C12 | 97.75 (13) | C1—Zr—C3—C4 | −75.40 (15) |
C1—Zr—Si—C12 | 66.10 (13) | Si—Zr—C3—C4 | 126.99 (17) |
C3—Si—N1—C13 | −167.0 (2) | N3—Zr—C3—Si | −89.67 (11) |
C11—Si—N1—C13 | 77.2 (2) | N2—Zr—C3—Si | 106.89 (12) |
C12—Si—N1—C13 | −51.4 (2) | N1—Zr—C3—Si | 6.99 (8) |
Zr—Si—N1—C13 | −176.7 (3) | C4—Zr—C3—Si | −126.99 (17) |
C3—Si—N1—Zr | 9.75 (11) | C2—Zr—C3—Si | 121.85 (16) |
C11—Si—N1—Zr | −106.08 (12) | C5—Zr—C3—Si | −163.09 (13) |
C12—Si—N1—Zr | 125.32 (12) | C1—Zr—C3—Si | 157.60 (13) |
N3—Zr—N1—C13 | −75.1 (2) | C2—C3—C4—C5 | −3.2 (3) |
N2—Zr—N1—C13 | 38.8 (2) | Si—C3—C4—C5 | 145.24 (18) |
C3—Zr—N1—C13 | 168.9 (2) | Zr—C3—C4—C5 | 67.66 (16) |
C4—Zr—N1—C13 | −167.6 (2) | C2—C3—C4—Zr | −70.87 (15) |
C2—Zr—N1—C13 | 138.8 (2) | Si—C3—C4—Zr | 77.57 (17) |
C5—Zr—N1—C13 | 178.68 (19) | N3—Zr—C4—C5 | 96.88 (15) |
C1—Zr—N1—C13 | 142.0 (2) | N2—Zr—C4—C5 | −23.3 (2) |
Si—Zr—N1—C13 | 176.7 (3) | N1—Zr—C4—C5 | −158.25 (14) |
N3—Zr—N1—Si | 108.17 (11) | C3—Zr—C4—C5 | −115.2 (2) |
N2—Zr—N1—Si | −137.84 (10) | C2—Zr—C4—C5 | −75.85 (15) |
C3—Zr—N1—Si | −7.79 (9) | C1—Zr—C4—C5 | −36.33 (13) |
C4—Zr—N1—Si | 15.75 (10) | Si—Zr—C4—C5 | −148.57 (15) |
C2—Zr—N1—Si | −37.84 (10) | N3—Zr—C4—C3 | −147.93 (15) |
C5—Zr—N1—Si | 1.99 (14) | N2—Zr—C4—C3 | 91.87 (19) |
C1—Zr—N1—Si | −34.64 (13) | N1—Zr—C4—C3 | −43.06 (14) |
N3—Zr—N2—C17 | −175.9 (3) | C2—Zr—C4—C3 | 39.33 (13) |
N1—Zr—N2—C17 | 71.2 (3) | C5—Zr—C4—C3 | 115.2 (2) |
C3—Zr—N2—C17 | −11.0 (3) | C1—Zr—C4—C3 | 78.86 (15) |
C4—Zr—N2—C17 | −60.2 (3) | Si—Zr—C4—C3 | −33.38 (12) |
C2—Zr—N2—C17 | −19.3 (3) | C3—C4—C5—C1 | 2.5 (3) |
C5—Zr—N2—C17 | −73.4 (3) | Zr—C4—C5—C1 | 66.28 (16) |
C1—Zr—N2—C17 | −49.9 (3) | C3—C4—C5—C6 | 167.7 (3) |
Si—Zr—N2—C17 | 41.3 (3) | Zr—C4—C5—C6 | −128.5 (4) |
N3—Zr—N2—C18 | 1.8 (3) | C3—C4—C5—Zr | −63.74 (16) |
N1—Zr—N2—C18 | −111.0 (3) | C2—C1—C5—C4 | −0.9 (3) |
C3—Zr—N2—C18 | 166.8 (2) | C9—C1—C5—C4 | 170.5 (2) |
C4—Zr—N2—C18 | 117.6 (3) | Zr—C1—C5—C4 | −64.33 (16) |
C2—Zr—N2—C18 | 158.4 (2) | C2—C1—C5—C6 | −171.7 (2) |
C5—Zr—N2—C18 | 104.4 (2) | C9—C1—C5—C6 | −0.3 (3) |
C1—Zr—N2—C18 | 127.9 (3) | Zr—C1—C5—C6 | 124.83 (17) |
Si—Zr—N2—C18 | −140.9 (2) | C2—C1—C5—Zr | 63.47 (17) |
N2—Zr—N3—C20 | 64.7 (3) | C9—C1—C5—Zr | −125.16 (17) |
N1—Zr—N3—C20 | −178.8 (3) | N3—Zr—C5—C4 | −84.68 (16) |
C3—Zr—N3—C20 | −102.7 (3) | N2—Zr—C5—C4 | 165.25 (14) |
C4—Zr—N3—C20 | −83.1 (3) | N1—Zr—C5—C4 | 26.61 (17) |
C2—Zr—N3—C20 | −73.0 (4) | C3—Zr—C5—C4 | 37.99 (14) |
C5—Zr—N3—C20 | −51.3 (3) | C2—Zr—C5—C4 | 79.79 (15) |
C1—Zr—N3—C20 | −38.6 (3) | C1—Zr—C5—C4 | 115.7 (2) |
Si—Zr—N3—C20 | −144.3 (3) | Si—Zr—C5—C4 | 27.70 (13) |
N2—Zr—N3—C19 | −137.3 (3) | N3—Zr—C5—C1 | 159.63 (15) |
N1—Zr—N3—C19 | −20.9 (3) | N2—Zr—C5—C1 | 49.56 (16) |
C3—Zr—N3—C19 | 55.2 (3) | N1—Zr—C5—C1 | −89.08 (15) |
C4—Zr—N3—C19 | 74.8 (3) | C3—Zr—C5—C1 | −77.70 (15) |
C2—Zr—N3—C19 | 85.0 (3) | C4—Zr—C5—C1 | −115.7 (2) |
C5—Zr—N3—C19 | 106.6 (3) | C2—Zr—C5—C1 | −35.90 (14) |
C1—Zr—N3—C19 | 119.3 (3) | Si—Zr—C5—C1 | −87.99 (13) |
Si—Zr—N3—C19 | 13.6 (3) | N3—Zr—C5—C6 | 59.6 (2) |
N3—Zr—C1—C2 | −141.35 (15) | N2—Zr—C5—C6 | −50.4 (2) |
N2—Zr—C1—C2 | 107.66 (15) | N1—Zr—C5—C6 | 170.93 (19) |
N1—Zr—C1—C2 | −6.11 (16) | C3—Zr—C5—C6 | −177.7 (2) |
C3—Zr—C1—C2 | −37.92 (13) | C4—Zr—C5—C6 | 144.3 (3) |
C4—Zr—C1—C2 | −79.98 (15) | C2—Zr—C5—C6 | −135.9 (2) |
C5—Zr—C1—C2 | −116.6 (2) | C1—Zr—C5—C6 | −100.0 (2) |
Si—Zr—C1—C2 | −24.39 (13) | Si—Zr—C5—C6 | 172.0 (2) |
N3—Zr—C1—C5 | −24.71 (18) | C4—C5—C6—C10 | 161.8 (3) |
N2—Zr—C1—C5 | −135.70 (15) | C1—C5—C6—C10 | −33.0 (2) |
N1—Zr—C1—C5 | 110.53 (14) | Zr—C5—C6—C10 | 50.5 (3) |
C3—Zr—C1—C5 | 78.72 (15) | C4—C5—C6—C7 | −95.0 (4) |
C4—Zr—C1—C5 | 36.66 (13) | C1—C5—C6—C7 | 70.3 (2) |
C2—Zr—C1—C5 | 116.6 (2) | Zr—C5—C6—C7 | 153.73 (17) |
Si—Zr—C1—C5 | 92.25 (13) | C5—C6—C7—C8 | −67.8 (2) |
N3—Zr—C1—C9 | 73.9 (2) | C10—C6—C7—C8 | 35.7 (2) |
N2—Zr—C1—C9 | −37.1 (2) | C6—C7—C8—C9 | −0.1 (3) |
N1—Zr—C1—C9 | −150.90 (19) | C2—C1—C9—C10 | −160.5 (3) |
C3—Zr—C1—C9 | 177.3 (2) | C5—C1—C9—C10 | 33.5 (2) |
C4—Zr—C1—C9 | 135.2 (2) | Zr—C1—C9—C10 | −48.4 (2) |
C2—Zr—C1—C9 | −144.8 (3) | C2—C1—C9—C8 | 96.2 (4) |
C5—Zr—C1—C9 | 98.6 (2) | C5—C1—C9—C8 | −69.8 (2) |
Si—Zr—C1—C9 | −169.2 (2) | Zr—C1—C9—C8 | −151.65 (18) |
C5—C1—C2—C3 | −1.2 (3) | C7—C8—C9—C1 | 67.9 (2) |
C9—C1—C2—C3 | −167.1 (3) | C7—C8—C9—C10 | −35.5 (2) |
Zr—C1—C2—C3 | 63.64 (16) | C5—C6—C10—C9 | 50.9 (2) |
C5—C1—C2—Zr | −64.82 (17) | C7—C6—C10—C9 | −57.0 (2) |
C9—C1—C2—Zr | 129.3 (4) | C1—C9—C10—C6 | −51.1 (2) |
N3—Zr—C2—C1 | 63.4 (2) | C8—C9—C10—C6 | 57.0 (2) |
N2—Zr—C2—C1 | −75.61 (15) | Si—N1—C13—C16A | −34.1 (4) |
N1—Zr—C2—C1 | 174.62 (14) | Zr—N1—C13—C16A | 149.9 (3) |
C3—Zr—C2—C1 | 115.4 (2) | Si—N1—C13—C14A | −161.4 (2) |
C4—Zr—C2—C1 | 75.94 (15) | Zr—N1—C13—C14A | 22.6 (4) |
C5—Zr—C2—C1 | 35.98 (13) | Si—N1—C13—C15A | 85.3 (3) |
Si—Zr—C2—C1 | 151.93 (15) | Zr—N1—C13—C15A | −90.6 (3) |
N3—Zr—C2—C3 | −52.1 (2) | Si—N1—C13—C15B | 152.5 (13) |
N2—Zr—C2—C3 | 168.96 (14) | Zr—N1—C13—C15B | −23.5 (13) |
N1—Zr—C2—C3 | 59.18 (14) | Si—N1—C13—C16B | 10.8 (9) |
C4—Zr—C2—C3 | −39.49 (13) | Zr—N1—C13—C16B | −165.1 (9) |
C5—Zr—C2—C3 | −79.46 (14) | Si—N1—C13—C14B | −92.5 (8) |
C1—Zr—C2—C3 | −115.4 (2) | Zr—N1—C13—C14B | 91.5 (8) |
Si—Zr—C2—C3 | 36.49 (11) |
Experimental details
Crystal data | |
Chemical formula | [Zr(C16H25NSi)(C2H6N)2] |
Mr | 438.84 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 150 |
a, b, c (Å) | 10.593 (1), 15.134 (2), 28.592 (3) |
V (Å3) | 4583.7 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.54 |
Crystal size (mm) | 0.35 × 0.31 × 0.19 |
Data collection | |
Diffractometer | Nonius Kappa CCD aarea-detector diffractometer |
Absorption correction | Multi-scan HKL SCALEPACK (Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.849, 0.902 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41422, 4038, 3443 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.080, 1.04 |
No. of reflections | 4038 |
No. of parameters | 251 |
No. of restraints | 3 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.80, −0.41 |
Computer programs: COLLECT (Nonius, 1999), DENZO (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEPII (Johnson, 1976), PLATON (Spek, 1990).
Zr—N3 | 2.048 (2) | N1—C13 | 1.478 (3) |
Zr—N2 | 2.059 (2) | N2—C17 | 1.433 (4) |
Zr—N1 | 2.107 (2) | N2—C18 | 1.452 (4) |
Si—N1 | 1.727 (2) | N3—C20 | 1.410 (4) |
Si—C3 | 1.864 (2) | N3—C19 | 1.506 (5) |
N3—Zr—N2 | 106.42 (10) | C17—N2—Zr | 125.0 (2) |
N3—Zr—N1 | 104.71 (9) | C18—N2—Zr | 125.1 (2) |
N2—Zr—N1 | 110.00 (9) | C20—N3—C19 | 107.4 (3) |
N1—Si—C3 | 95.55 (10) | C20—N3—Zr | 123.1 (2) |
C13—N1—Si | 127.19 (17) | C19—N3—Zr | 126.5 (2) |
C13—N1—Zr | 128.52 (16) | C2—C3—C4 | 106.5 (2) |
Si—N1—Zr | 104.21 (9) | C2—C3—Si | 120.33 (17) |
C17—N2—C18 | 109.9 (3) | C4—C3—Si | 125.17 (18) |
Cg-Zr | 2.2352 (10) |
Cg-Zr-N1 | 100.26 (6) |
Cg-Zr-N2 | 118.16 (7) |
Cg-Zr-N3 | 116.26 (8) |
Cg is the ring centroid for atoms C1, C2, C3, C4 and C5. |
There is considerable industrial interest in Group 4 half-sandwich complexes containing linked amido cyclopentadienyl (Cp) ligands, as catalysts for ethylene and propylene polymerization. The classical preparative route via amido dilithium salts and ZrCl4 or TiCl3(THF)3 in combination leads to low isolated yields of product mixtures with non-substituted Cp ligands. Alternatively, such complexes can be prepared by an amine-elimination reaction with excellent efficiency (Hughes et al., 1993; Herrmann & Morawietz, 1994; Carpenetti et al., 1996; Leung et al., 1999). We have previously demonstrated that the `constrained geometry' complex [isodiCpSiMe2N-tert-butyl]ZrCl2 can be synthesized by the classical metathesis route in 55% yield (Gentil et al., 2000). In this paper, we report the high-yield `one pot' formation of [isodiCpSiMe2N-tert-butyl]Zr(NMe2)2, (I), and its X-ray structure. Complex (I) was obtained according to the amine-elimination pathway developed earlier (Hughes et al., 1993; Herrmann & Morawietz, 1994; Carpenetti et al., 1996; Leung et al., 1999), using Zr(NMe2)4 and the corresponding amine as starting materials. \sch
As expected on the basis of experimental reaction conditions and prior results in this field (Paquette et al., 1989; Sornay et al., 1991; Zaegel et al., 1995; Gobley et al., 1998; Gentil et al., 2000, 2002), the molecular structure of (I) indicates that exo complexation of the isodicyclopentadienyl ligand to Zr has occurred. This structure exhibits the classical half-sandwich pseudotetrahedral geometry about the Zr atom. Comparison with [isodiCpSiMe2N-tert-butyl]Zr(CH2SiMe3)2 (Gentil et al., 2000) provides indications as to the structural changes due to the two –CH2SiMe3 substituents being replaced by the dimethylamino groups. The presence of the –NMe2 groups significantly increases both the Cg—Zr distance (Cg is the ring centroid for C1/C2/C3/C4/C5) and the Zr—N1 bond length. The Cg—Zr distance is 2.2125 (8) Å and the Zr—N bond length is 2.0858 (14) Å for [isodiCpSiMe2N-tert-butyl]Zr(CH2SiMe3)2, whereas these values are 2.2352 (10) and 2.107 (2) Å, respectively, for (I). The values for this structure agree well with those in the analogous complex [C5Me4SiMe2N-tert-butyl]Zr(NMe2)2 (Carpenetti et al., 1996), where Cg—Zr is 2.233 (3) Å and Zr—N1 is 2.108 (4) Å.
As observed in previous structures containing an isodicyclopentadienyl ligand with exo complexation, there is a small amount of bending in this ligand about the bond common to the Cp ring and the norbornane fragment. The dihedral angle between the least-squares planes defined by C1/C2/C3/C4/C5 and C1/C5/C6/C9 is 8.1 (2)°, and this bending is in the endo direction.
The (isodiCp)SiMe2N-tert-butyl ligand in (I) has a constrained geometry, characterized by the small angle of 95.55 (10)° for N1—Si—C3 and by the displacement of the Si atom from its adjacent Cp ring, measured by the angle of 27.4 (1)° between the Si—C3 bond and the plane of the Cp ring. The sum of the angles about atom N1 is 359.9 (3)°, indicative of sp2 hybridization.