ansa-[(tert-Butylamino)(isodicyclo­pentadienyl)dimethylsilane]Zr(NMe₂)₂ prepared by an amine-elimination reaction

An amine-elimination reaction was used to obtain the title compound, i.e. (N-tert-butyl-N-{[(1,2,3,3a,7a-η)-4,5,6,7-tetra­hydro-4,7-methano-1H-inden-2-yl]­di­methyl­silyl}amido-κN)bis(N-methyl­methanaminato-κN)­zirconium(IV) or [isodiCpSiMe₂N-tert-butyl]Zr(NMe₂)₂ (Cp is cyclo­penta­dienyl), [Zr(C₁₆H₂₅NSi)(C₂H₆N)₂], in very good yield. Treatment of isodiCpHSiMe₂NH-tert-butyl with Zr(NMe₂)₄ leads to the formation of a yellow solid that can be purified by sublimation. The single-crystal structure of the product shows the exo complexation of the isodi­cyclo­penta­dienyl ligand to the Zr atom. The Cp portion of this ligand is bonded to the Zr atom in a η⁵ manner, with a Zr—Cg (Cg is the ring centroid) distance of 2.2352 (10) Å. The isodiCpSiMe₂N-tert-butyl ligand has a constrained geometry, which is exhibited by the small angle of 95.55 (10)° for N—Si—C_Cp.

S1. Comment

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 [isodiCpSiMe<sub>2</sub>N-tert-butyl]ZrCl<sub>2</sub> 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.

S2. Experimental

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.

S3. Refinement

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 U_iso(H) = 1.5U_eq(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 U_iso(H) = 1.2U_eq(C).

Computing details

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).

Figures

Fig. 1. A view of the structure of (I), drawn with 40% probability displacement ellipsoids. Only the major component of the disordered tert-butyl group is shown, for clarity. H atoms are shown as small spheres of arbitrary radii.

(N-tert-butyl-N-{[(1,2,3,3a,7a-η)-4,5,6,7-tetrahydro-4,7-methano-1H-inden- 2-yl]dimethylsilyl}amido)-κN]bis(N-methylmethanaminato-κN)zirconium(IV)

Crystal data

[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) Å^3	Rectangular block, colourless
Z = 8	0.35 × 0.31 × 0.19 mm

Data collection

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

Refinement on F^2	Primary atom site location: heavy-atom method
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.080	H-atom parameters constrained
S = 1.04	w = 1/[σ^2(Fo^2) + (0.0361P)^2 + 6.0948P] where P = (Fo^2 + 2Fc^2)/3
4038 reflections	(Δ/σ)max = 0.010
251 parameters	Δρmax = 0.80 e Å^−3
3 restraints	Δρmin = −0.41 e Å^−3

Special details

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, ²J_HH = 8.93 Hz, anti-methano bridge), 1.45 (s, 9H, NC(CH₃)₃), 1.20 (d, 2H, ²J_HH = 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	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*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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)