Tri­benzyl([eta]⁵-penta­methyl­cyclo­penta­dienyl)­hafnium(IV)

The title compound, [Hf(C₇H₇)₃(C₁₀H₁₅)], adopts a monomeric three-legged piano-stool structure. One benzyl ligand is disordered between two sites (44:56%) related by a ~30° rotation about an axis defined by the Hf atom and the ipso-C atom of the benzyl ligand.

S1. Comment

The structures of electronically unsaturated early transition metal benzyl complexes are often distorted by weak M—Ph interactions which lead to reduced M—CH₂—Ph angles and short M···C_ipso contacts. Such η²– or ηⁿ-benzyl structures were first observed for M(CH₂Ph)₄ (M = Ti, Zr, Hf) complexes (Davies et al., 1971; Bassi et al., 1971) and have since been observed in a variety of systems, including cationic group 4 metal benzyl compounds (Jordan et al., 1987, 1990; Crowther et al., 1993; Bei et al., 1997).

The title compound, (I), adopts a monomeric three-legged piano-stool structure. The plane formed by the three methylene C atoms (C11, C21A and C21B average, and C31) is parallel to the pentamethylcyclopentadienyl (Cp*) plane (dihedral angle = 0.5°). The Cp* methyl groups are bent slightly away from the Hf atom, with the largest deviation [0.166 (10) Å from the C1–C5 plane] occurring with the C10-methyl group that is eclipsed with the disordered benzyl ligand [C21A—C27A, occupancy = 0.44 (3); C21B–C27B, occupancy = 0.56 (3)]. There are no short Hf···C_ipso contacts (no distances less than 3.1 Å), indicating no significant Hf—Ph interaction.

S2. Experimental

A solution of PhCH₂MgCl (10.2 ml, 2.0 M in tetrahydrofuran, 20.4 mmol) was added to a slurry of Cp*HfCl₃ (2.60 g, 6.19 mmol) in Et₂O (30 ml) at 195 K under nitrogen. The reaction mixture was warmed to room temperature and stirred for 1 h, resulting in a pale-yellow slurry. The solvent was removed under vacuum and the resultant solid was extracted with hexane (3 x 40 ml), giving a yellow filtrate. The filtrate was evaporated under vacuum to give a yellow solid which was further purified by recrystallization from toluene/hexane (1.34 g, 36.3%). Crystals suitable for X-ray diffraction were grown from a saturated toluene/hexane solution cooled to 238 K. Analysis calculated for C₃₁H₃₆Hf: C 64.42, H 6.18; found: C 64.50, H 5.99%. ¹H NMR (C₆D₆, 298 K) δ 7.14 (t, J = 7.6 Hz, 6H, meta), 6.91 (t, J = 7.6 Hz, 3H, para), 6.66 (d, J = 7.2 Hz, 6H, ortho), 1.7 (s, 15H, Cp*), 1.68 (s, 6H, CH₂). The low temperature ¹H NMR spectrum (toluene-d₈, 203 K) is essentially unchanged from that at ambient temperature. ¹³C{H} NMR (C₆D₆, 298 K): δ 145.9 (ipso-Ph), 128.8, 128.3, 122.9, 119.3 (C₅Me₅), 83.8 (t, J_CH = 121.4 Hz, from gated-{¹H} spectrum, HfCH₂), 11.7 (C₅Me₅).

S3. Refinement

One benzyl ligand (designated with C2** labels) was found to be disordered with two orientations; one is related to the other by a rotation of ~30° about an axis approximated by the Hf—(C22A/C22B average) direction. The occupancies refined to 0.44 (3) for the C2*A site and 0.56 (3) for the C2*B site. Each ligand was refined with individual anisotropic displacement parameters subject to the following restraints: (i) the ring C—C bonds were restrained to 1.39 (1) Å; (ii) the C22A and C22B atoms were assigned the same thermal displacement due to their close proximity (0.138 Å); (iii) each partial benzyl group was restrained to be flat (s.u. = 0.1); (iv) the rigid-bond restraint (s.u. = 0.005) was applied to the displacement parameters of each partially occupied benzyl group; (v) displacement parameters of atoms between the two sites were restrained to be similar if within 0.6 Å (s.u. = 0.05); (iv)) the two sites were restrained to have the same conformation and bonds on opposite sides of the phenyl rings were restrained to be the same (default s.u.'s). H atoms were included with the riding model using program defaults.

Computing details

Data collection: CAD-4 Operations Manual (Enraf-Nonius, 1977); cell refinement: CAD-4 Operations Manual; data reduction: MolEN (Fair, 1990); program(s) used to solve structure: SHELXTL (Sheldrick, 1995); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

(I)

Crystal data

[Hf(C7H7)3(C10H15)]	Z = 2
Mr = 587.09	F(000) = 588
Triclinic, P1	Dx = 1.487 Mg m^−3
a = 10.359 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 12.693 (2) Å	Cell parameters from 40 reflections
c = 10.102 (7) Å	θ = 6.5–10.2°
α = 97.49 (3)°	µ = 3.99 mm^−1
β = 91.42 (2)°	T = 293 K
γ = 94.96 (1)°	Prism, yellow
V = 1311.1 (9) Å^3	0.56 × 0.42 × 0.40 mm

Data collection

Enraf-Nonius CAD-4 diffractometer	3907 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.017
Graphite monochromator	θmax = 25.0°, θmin = 1.5°
θ–2θ scans	h = −12→12
Absorption correction: ψ scans (MolEN; Fair, 1990)	k = −15→15
Tmin = 0.154, Tmax = 0.202	l = −11→11
8828 measured reflections	4 standard reflections every 60 min
4414 independent reflections	intensity decay: <2%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.029	H-atom parameters constrained
wR(F^2) = 0.079	Calculated w = 1/[σ^2(Fo^2) + (0.0428P)^2 + 1.4361P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = −0.031
4414 reflections	Δρmax = 0.83 e Å^−3
353 parameters	Δρmin = −1.01 e Å^−3
105 restraints	Extinction correction: SHELXTL, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0117 (11)

Special details

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 on F² for ALL reflections except for 0 with very negative F² or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R-factor-obs 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)
Hf1	0.20408 (2)	0.29708 (2)	0.69427 (2)	0.06052 (13)
C1	0.1191 (5)	0.4744 (4)	0.6845 (6)	0.0725 (13)
C2	0.0087 (5)	0.3998 (5)	0.6832 (6)	0.0729 (14)
C3	0.0071 (5)	0.3289 (4)	0.5626 (5)	0.0664 (12)
C4	0.1164 (5)	0.3602 (4)	0.4902 (5)	0.0648 (12)
C5	0.1841 (5)	0.4502 (4)	0.5651 (5)	0.0669 (12)
C6	0.1560 (7)	0.5677 (5)	0.7906 (7)	0.100 (2)
H6A	0.0925	0.5699	0.8584	0.150*
H6B	0.1596	0.6327	0.7512	0.150*
H6C	0.2394	0.5601	0.8300	0.150*
C7	−0.0962 (6)	0.4022 (7)	0.7840 (7)	0.103 (2)
H7A	−0.1636	0.4429	0.7563	0.154*
H7B	−0.0602	0.4347	0.8697	0.154*
H7C	−0.1317	0.3307	0.7903	0.154*
C8	−0.0981 (5)	0.2427 (5)	0.5147 (7)	0.090 (2)
H8A	−0.0632	0.1887	0.4541	0.135*
H8B	−0.1661	0.2726	0.4698	0.135*
H8C	−0.1323	0.2117	0.5897	0.135*
C9	0.1513 (6)	0.3094 (5)	0.3557 (6)	0.085 (2)
H9A	0.1302	0.3538	0.2897	0.127*
H9B	0.1035	0.2407	0.3352	0.127*
H9C	0.2425	0.3011	0.3558	0.127*
C10	0.2975 (6)	0.5171 (5)	0.5177 (7)	0.088 (2)
H10A	0.3499	0.5514	0.5934	0.132*
H10B	0.2657	0.5702	0.4689	0.132*
H10C	0.3487	0.4721	0.4607	0.132*
C11	0.1776 (5)	0.1280 (4)	0.5943 (6)	0.0776 (14)
H11A	0.1021	0.1195	0.5338	0.093*
H11B	0.2525	0.1132	0.5417	0.093*
C12	0.1608 (5)	0.0502 (4)	0.6903 (6)	0.0666 (12)
C13	0.0384 (5)	0.0189 (5)	0.7356 (7)	0.083 (2)
H13	−0.0341	0.0473	0.7035	0.100*
C14	0.0231 (8)	−0.0519 (6)	0.8251 (8)	0.108 (2)
H14	−0.0593	−0.0706	0.8537	0.129*
C15	0.1283 (10)	−0.0964 (6)	0.8741 (8)	0.109 (2)
H15	0.1177	−0.1455	0.9345	0.130*
C16	0.2495 (8)	−0.0662 (6)	0.8313 (7)	0.099 (2)
H16	0.3216	−0.0951	0.8634	0.119*
C17	0.2648 (5)	0.0059 (5)	0.7422 (6)	0.0763 (14)
H17	0.3478	0.0257	0.7158	0.092*
C21A	0.411 (2)	0.331 (2)	0.646 (3)	0.068 (5)	0.44 (3)
H21A	0.4156	0.3323	0.5502	0.081*	0.44 (3)
H21B	0.4417	0.4014	0.6896	0.081*	0.44 (3)
C22A	0.502 (4)	0.254 (3)	0.685 (2)	0.0653 (13)	0.44 (3)
C23A	0.537 (4)	0.170 (2)	0.594 (3)	0.083 (6)	0.44 (3)
H23A	0.5043	0.1626	0.5065	0.100*	0.44 (3)
C24A	0.619 (4)	0.098 (2)	0.631 (4)	0.101 (8)	0.44 (3)
H24A	0.6424	0.0431	0.5677	0.121*	0.44 (3)
C25A	0.666 (3)	0.106 (2)	0.761 (4)	0.108 (9)	0.44 (3)
H25A	0.7175	0.0556	0.7874	0.129*	0.44 (3)
C26A	0.635 (2)	0.190 (3)	0.852 (3)	0.103 (8)	0.44 (3)
H26A	0.6691	0.1980	0.9391	0.123*	0.44 (3)
C27A	0.554 (2)	0.262 (2)	0.813 (2)	0.077 (5)	0.44 (3)
H27A	0.5340	0.3185	0.8758	0.092*	0.44 (3)
C21B	0.422 (2)	0.3485 (14)	0.700 (3)	0.074 (4)	0.56 (3)
H21C	0.4416	0.3850	0.6231	0.089*	0.56 (3)
H21D	0.4442	0.3983	0.7798	0.089*	0.56 (3)
C22B	0.501 (3)	0.255 (2)	0.698 (2)	0.0653 (13)	0.56 (3)
C23B	0.531 (3)	0.196 (2)	0.578 (2)	0.083 (4)	0.56 (3)
H23B	0.5017	0.2159	0.4978	0.100*	0.56 (3)
C24B	0.603 (3)	0.110 (2)	0.577 (2)	0.093 (5)	0.56 (3)
H24B	0.6223	0.0720	0.4951	0.111*	0.56 (3)
C25B	0.647 (2)	0.079 (2)	0.692 (2)	0.093 (5)	0.56 (3)
H25B	0.6942	0.0194	0.6896	0.111*	0.56 (3)
C26B	0.620 (2)	0.134 (2)	0.811 (2)	0.091 (4)	0.56 (3)
H26B	0.6518	0.1152	0.8906	0.109*	0.56 (3)
C27B	0.546 (2)	0.220 (2)	0.8118 (14)	0.072 (3)	0.56 (3)
H27B	0.5260	0.2559	0.8939	0.086*	0.56 (3)
C31	0.1577 (6)	0.3036 (5)	0.9147 (5)	0.081 (2)
H31A	0.1240	0.3715	0.9434	0.098*
H31B	0.0891	0.2481	0.9231	0.098*
C32	0.2657 (5)	0.2911 (4)	1.0063 (5)	0.0668 (12)
C33	0.3469 (6)	0.3786 (4)	1.0647 (6)	0.0756 (14)
H33	0.3324	0.4464	1.0455	0.091*
C34	0.4478 (7)	0.3667 (6)	1.1502 (7)	0.093 (2)
H34	0.5001	0.4267	1.1886	0.111*
C35	0.4734 (7)	0.2686 (6)	1.1801 (7)	0.097 (2)
H35	0.5419	0.2613	1.2385	0.116*
C36	0.3958 (7)	0.1813 (5)	1.1222 (7)	0.091 (2)
H36	0.4118	0.1137	1.1409	0.109*
C37	0.2946 (6)	0.1928 (4)	1.0366 (6)	0.0757 (14)
H37	0.2437	0.1321	0.9978	0.091*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Hf1	0.05347 (15)	0.0619 (2)	0.0662 (2)	0.00708 (8)	0.00792 (9)	0.00636 (9)
C1	0.071 (3)	0.070 (3)	0.075 (3)	0.018 (2)	−0.002 (3)	−0.002 (2)
C2	0.060 (3)	0.084 (3)	0.079 (4)	0.023 (2)	0.015 (3)	0.011 (3)
C3	0.051 (2)	0.078 (3)	0.070 (3)	0.011 (2)	−0.004 (2)	0.010 (2)
C4	0.064 (3)	0.069 (3)	0.062 (3)	0.012 (2)	0.001 (2)	0.008 (2)
C5	0.064 (3)	0.063 (3)	0.075 (3)	0.007 (2)	0.002 (2)	0.013 (2)
C6	0.111 (5)	0.080 (4)	0.104 (5)	0.025 (4)	0.000 (4)	−0.013 (3)
C7	0.070 (4)	0.142 (6)	0.103 (5)	0.041 (4)	0.029 (3)	0.018 (4)
C8	0.058 (3)	0.093 (4)	0.116 (5)	0.001 (3)	−0.008 (3)	0.010 (4)
C9	0.092 (4)	0.101 (4)	0.061 (3)	0.013 (3)	0.006 (3)	0.004 (3)
C10	0.081 (4)	0.076 (4)	0.110 (5)	−0.003 (3)	0.005 (3)	0.031 (3)
C11	0.067 (3)	0.068 (3)	0.096 (4)	0.008 (2)	0.007 (3)	0.003 (3)
C12	0.060 (3)	0.056 (3)	0.080 (3)	0.003 (2)	0.008 (2)	−0.008 (2)
C13	0.062 (3)	0.072 (3)	0.109 (5)	0.000 (2)	0.012 (3)	−0.007 (3)
C14	0.107 (5)	0.090 (5)	0.116 (6)	−0.027 (4)	0.041 (5)	−0.010 (4)
C15	0.159 (8)	0.073 (4)	0.089 (5)	−0.005 (5)	0.016 (5)	0.004 (3)
C16	0.111 (5)	0.091 (4)	0.097 (5)	0.023 (4)	0.002 (4)	0.006 (4)
C17	0.068 (3)	0.076 (3)	0.083 (4)	0.010 (3)	0.008 (3)	0.000 (3)
C21A	0.047 (5)	0.061 (8)	0.090 (14)	−0.003 (5)	−0.006 (8)	−0.003 (9)
C22A	0.046 (2)	0.070 (3)	0.080 (4)	−0.003 (2)	0.015 (3)	0.013 (3)
C23A	0.057 (10)	0.073 (11)	0.117 (10)	0.006 (8)	0.014 (10)	−0.001 (8)
C24A	0.07 (2)	0.079 (11)	0.16 (2)	0.016 (9)	0.03 (2)	0.023 (16)
C25A	0.086 (16)	0.087 (15)	0.17 (3)	0.025 (13)	0.029 (16)	0.056 (15)
C26A	0.085 (12)	0.13 (2)	0.115 (12)	0.037 (14)	0.031 (9)	0.060 (13)
C27A	0.059 (8)	0.084 (14)	0.091 (6)	0.008 (10)	0.009 (6)	0.024 (7)
C21B	0.060 (4)	0.069 (8)	0.093 (13)	−0.006 (5)	−0.002 (8)	0.014 (7)
C22B	0.046 (2)	0.070 (3)	0.080 (4)	−0.003 (2)	0.015 (3)	0.013 (3)
C23B	0.059 (9)	0.109 (15)	0.079 (5)	0.000 (9)	0.018 (6)	0.004 (6)
C24B	0.065 (9)	0.104 (12)	0.102 (8)	0.003 (7)	0.027 (9)	−0.017 (9)
C25B	0.059 (9)	0.091 (11)	0.127 (12)	0.009 (7)	0.020 (10)	0.002 (9)
C26B	0.088 (11)	0.080 (10)	0.106 (8)	0.015 (8)	0.000 (8)	0.013 (8)
C27B	0.067 (7)	0.069 (9)	0.080 (5)	0.001 (6)	0.015 (5)	0.015 (5)
C31	0.083 (4)	0.100 (4)	0.060 (3)	0.008 (3)	0.009 (3)	0.004 (3)
C32	0.069 (3)	0.071 (3)	0.058 (3)	0.002 (2)	0.013 (2)	−0.001 (2)
C33	0.087 (4)	0.066 (3)	0.071 (3)	0.004 (3)	0.006 (3)	−0.002 (2)
C34	0.091 (4)	0.091 (4)	0.084 (4)	−0.008 (3)	−0.002 (3)	−0.019 (3)
C35	0.093 (4)	0.121 (6)	0.076 (4)	0.018 (4)	−0.006 (3)	0.007 (4)
C36	0.104 (5)	0.085 (4)	0.088 (4)	0.022 (3)	0.018 (4)	0.018 (3)
C37	0.084 (4)	0.068 (3)	0.072 (3)	−0.005 (3)	0.015 (3)	0.003 (3)

Geometric parameters (Å, º)

Hf1—C11	2.240 (5)	C16—C17	1.367 (9)
Hf1—C21A	2.23 (3)	C16—H16	0.93
Hf1—C21B	2.29 (2)	C17—H17	0.93
Hf1—C31	2.282 (6)	C21A—C22A	1.492 (14)
Hf1—C4	2.486 (5)	C21A—H21A	0.97
Hf1—C5	2.499 (5)	C21A—H21B	0.97
Hf1—C3	2.499 (5)	C22A—C27A	1.383 (9)
Hf1—C1	2.500 (5)	C22A—C23A	1.387 (8)
Hf1—C2	2.508 (5)	C23A—C24A	1.385 (9)
C1—C5	1.408 (8)	C23A—H23A	0.93
C1—C2	1.419 (8)	C24A—C25A	1.379 (9)
C1—C6	1.506 (8)	C24A—H24A	0.93
C2—C3	1.416 (8)	C25A—C26A	1.376 (9)
C2—C7	1.507 (7)	C25A—H25A	0.93
C3—C4	1.419 (7)	C26A—C27A	1.384 (8)
C3—C8	1.499 (7)	C26A—H26A	0.93
C4—C5	1.407 (7)	C27A—H27A	0.93
C4—C9	1.492 (7)	C21B—C22B	1.500 (12)
C5—C10	1.513 (7)	C21B—H21C	0.97
C6—H6A	0.96	C21B—H21D	0.97
C6—H6B	0.96	C22B—C27B	1.368 (14)
C6—H6C	0.96	C22B—C23B	1.395 (13)
C7—H7A	0.96	C23B—C24B	1.383 (14)
C7—H7B	0.96	C23B—H23B	0.93
C7—H7C	0.96	C24B—C25B	1.36 (2)
C8—H8A	0.96	C24B—H24B	0.93
C8—H8B	0.96	C25B—C26B	1.36 (2)
C8—H8C	0.96	C25B—H25B	0.93
C9—H9A	0.96	C26B—C27B	1.385 (15)
C9—H9B	0.96	C26B—H26B	0.93
C9—H9C	0.96	C27B—H27B	0.93
C10—H10A	0.96	C31—C32	1.467 (8)
C10—H10B	0.96	C31—H31A	0.97
C10—H10C	0.96	C31—H31B	0.97
C11—C12	1.475 (8)	C32—C37	1.378 (8)
C11—H11A	0.97	C32—C33	1.390 (7)
C11—H11B	0.97	C33—C34	1.371 (9)
C12—C17	1.380 (8)	C33—H33	0.93
C12—C13	1.401 (7)	C34—C35	1.365 (10)
C13—C14	1.358 (10)	C34—H34	0.93
C13—H13	0.93	C35—C36	1.367 (10)
C14—C15	1.380 (11)	C35—H35	0.93
C14—H14	0.93	C36—C37	1.372 (9)
C15—C16	1.377 (11)	C36—H36	0.93
C15—H15	0.93	C37—H37	0.93
C21A—Hf1—C11	97.3 (6)	C12—C11—H11A	109.0
C21A—Hf1—C31	117.2 (7)	Hf1—C11—H11A	109.0
C11—Hf1—C31	110.0 (2)	C12—C11—H11B	109.0
C11—Hf1—C21B	106.8 (5)	Hf1—C11—H11B	109.0
C31—Hf1—C21B	103.4 (7)	H11A—C11—H11B	107.8
C21A—Hf1—C4	94.6 (6)	C17—C12—C13	116.5 (6)
C11—Hf1—C4	90.5 (2)	C17—C12—C11	121.9 (5)
C31—Hf1—C4	138.3 (2)	C13—C12—C11	121.6 (5)
C21B—Hf1—C4	104.8 (6)	C14—C13—C12	121.6 (6)
C21A—Hf1—C5	80.3 (5)	C14—C13—H13	119.2
C11—Hf1—C5	121.3 (2)	C12—C13—H13	119.2
C31—Hf1—C5	123.1 (2)	C13—C14—C15	120.9 (7)
C21B—Hf1—C5	84.6 (5)	C13—C14—H14	119.6
C4—Hf1—C5	32.8 (2)	C15—C14—H14	119.6
C21A—Hf1—C3	127.7 (6)	C16—C15—C14	118.4 (7)
C11—Hf1—C3	87.0 (2)	C16—C15—H15	120.8
C31—Hf1—C3	109.7 (2)	C14—C15—H15	120.8
C21B—Hf1—C3	137.0 (6)	C17—C16—C15	120.7 (7)
C4—Hf1—C3	33.1 (2)	C17—C16—H16	119.7
C5—Hf1—C3	54.5 (2)	C15—C16—H16	119.7
C21A—Hf1—C1	101.6 (5)	C16—C17—C12	122.0 (6)
C11—Hf1—C1	141.0 (2)	C16—C17—H17	119.0
C31—Hf1—C1	91.2 (2)	C12—C17—H17	119.0
C21B—Hf1—C1	99.2 (4)	C22A—C21A—Hf1	116 (3)
C4—Hf1—C1	54.5 (2)	C22A—C21A—H21A	108.3
C5—Hf1—C1	32.7 (2)	Hf1—C21A—H21A	108.3
C3—Hf1—C1	54.5 (2)	C22A—C21A—H21B	108.2
C21A—Hf1—C2	133.2 (5)	Hf1—C21A—H21B	108.3
C11—Hf1—C2	115.1 (2)	H21A—C21A—H21B	107.4
C31—Hf1—C2	83.6 (2)	C27A—C22A—C23A	116.8 (11)
C21B—Hf1—C2	132.1 (4)	C27A—C22A—C21A	121.3 (11)
C4—Hf1—C2	54.6 (2)	C23A—C22A—C21A	121.8 (12)
C5—Hf1—C2	54.4 (2)	C24A—C23A—C22A	121.9 (12)
C3—Hf1—C2	32.9 (2)	C24A—C23A—H23A	119.1
C1—Hf1—C2	32.9 (2)	C22A—C23A—H23A	119.0
C5—C1—C2	108.1 (5)	C25A—C24A—C23A	119.9 (14)
C5—C1—C6	125.6 (6)	C25A—C24A—H24A	120.1
C2—C1—C6	126.1 (6)	C23A—C24A—H24A	120.1
C5—C1—Hf1	73.6 (3)	C26A—C25A—C24A	119.4 (14)
C2—C1—Hf1	73.9 (3)	C26A—C25A—H25A	120.3
C6—C1—Hf1	121.4 (4)	C24A—C25A—H25A	120.3
C3—C2—C1	107.7 (5)	C25A—C26A—C27A	119.9 (13)
C3—C2—C7	125.6 (6)	C25A—C26A—H26A	120.0
C1—C2—C7	126.4 (6)	C27A—C26A—H26A	120.1
C3—C2—Hf1	73.2 (3)	C22A—C27A—C26A	122.1 (12)
C1—C2—Hf1	73.2 (3)	C22A—C27A—H27A	119.0
C7—C2—Hf1	124.3 (4)	C26A—C27A—H27A	118.9
C2—C3—C4	107.8 (5)	C22B—C21B—Hf1	111.9 (19)
C2—C3—C8	125.8 (5)	C22B—C21B—H21C	109.3
C4—C3—C8	126.2 (5)	Hf1—C21B—H21C	109.2
C2—C3—Hf1	73.9 (3)	C22B—C21B—H21D	109.2
C4—C3—Hf1	72.9 (3)	Hf1—C21B—H21D	109.2
C8—C3—Hf1	123.1 (4)	H21C—C21B—H21D	107.9
C5—C4—C3	108.1 (5)	C27B—C22B—C23B	115.7 (10)
C5—C4—C9	125.7 (5)	C27B—C22B—C21B	123.3 (11)
C3—C4—C9	126.2 (5)	C23B—C22B—C21B	121.0 (11)
C5—C4—Hf1	74.1 (3)	C24B—C23B—C22B	121.1 (11)
C3—C4—Hf1	74.0 (3)	C24B—C23B—H23B	119.5
C9—C4—Hf1	119.7 (4)	C22B—C23B—H23B	119.4
C4—C5—C1	108.3 (5)	C25B—C24B—C23B	121.0 (11)
C4—C5—C10	125.5 (5)	C25B—C24B—H24B	119.5
C1—C5—C10	125.8 (5)	C23B—C24B—H24B	119.5
C4—C5—Hf1	73.1 (3)	C24B—C25B—C26B	119.5 (12)
C1—C5—Hf1	73.7 (3)	C24B—C25B—H25B	120.2
C10—C5—Hf1	124.7 (4)	C26B—C25B—H25B	120.2
C1—C6—H6A	109.5	C25B—C26B—C27B	119.1 (12)
C1—C6—H6B	109.5	C25B—C26B—H26B	120.4
H6A—C6—H6B	109.5	C27B—C26B—H26B	120.4
C1—C6—H6C	109.5	C22B—C27B—C26B	123.5 (11)
H6A—C6—H6C	109.5	C22B—C27B—H27B	118.3
H6B—C6—H6C	109.5	C26B—C27B—H27B	118.2
C2—C7—H7A	109.5	C32—C31—Hf1	116.3 (4)
C2—C7—H7B	109.5	C32—C31—H31A	108.2
H7A—C7—H7B	109.5	Hf1—C31—H31A	108.2
C2—C7—H7C	109.5	C32—C31—H31B	108.2
H7A—C7—H7C	109.5	Hf1—C31—H31B	108.2
H7B—C7—H7C	109.5	H31A—C31—H31B	107.4
C3—C8—H8A	109.5	C37—C32—C33	116.4 (5)
C3—C8—H8B	109.5	C37—C32—C31	122.4 (5)
H8A—C8—H8B	109.5	C33—C32—C31	121.2 (5)
C3—C8—H8C	109.5	C34—C33—C32	121.1 (6)
H8A—C8—H8C	109.5	C34—C33—H33	119.5
H8B—C8—H8C	109.5	C32—C33—H33	119.5
C4—C9—H9A	109.5	C35—C34—C33	121.4 (6)
C4—C9—H9B	109.5	C35—C34—H34	119.3
H9A—C9—H9B	109.5	C33—C34—H34	119.3
C4—C9—H9C	109.5	C34—C35—C36	118.4 (6)
H9A—C9—H9C	109.5	C34—C35—H35	120.8
H9B—C9—H9C	109.5	C36—C35—H35	120.8
C5—C10—H10A	109.5	C35—C36—C37	120.5 (6)
C5—C10—H10B	109.5	C35—C36—H36	119.8
H10A—C10—H10B	109.5	C37—C36—H36	119.8
C5—C10—H10C	109.5	C36—C37—C32	122.2 (5)
H10A—C10—H10C	109.5	C36—C37—H37	118.9
H10B—C10—H10C	109.5	C32—C37—H37	118.9
C12—C11—Hf1	112.7 (4)
C21A—Hf1—C1—C5	50.5 (8)	C5—Hf1—C4—C9	122.4 (6)
C11—Hf1—C1—C5	−66.9 (4)	C3—Hf1—C4—C9	−122.9 (6)
C31—Hf1—C1—C5	168.6 (3)	C1—Hf1—C4—C9	159.3 (5)
C21B—Hf1—C1—C5	64.8 (7)	C2—Hf1—C4—C9	−160.0 (5)
C4—Hf1—C1—C5	−36.9 (3)	C3—C4—C5—C1	0.9 (6)
C5—Hf1—C1—C5	0.000 (2)	C9—C4—C5—C1	178.7 (5)
C3—Hf1—C1—C5	−77.9 (3)	Hf1—C4—C5—C1	−65.8 (4)
C2—Hf1—C1—C5	−115.0 (5)	C3—C4—C5—C10	−172.4 (5)
C21A—Hf1—C1—C2	165.5 (8)	C9—C4—C5—C10	5.5 (9)
C11—Hf1—C1—C2	48.2 (5)	Hf1—C4—C5—C10	120.9 (5)
C31—Hf1—C1—C2	−76.4 (4)	C3—C4—C5—Hf1	66.7 (4)
C21B—Hf1—C1—C2	179.8 (7)	C9—C4—C5—Hf1	−115.4 (5)
C4—Hf1—C1—C2	78.1 (3)	Hf1—C4—C5—Hf1	0.0
C5—Hf1—C1—C2	115.0 (5)	C2—C1—C5—C4	−0.9 (6)
C3—Hf1—C1—C2	37.2 (3)	C6—C1—C5—C4	−177.3 (5)
C2—Hf1—C1—C2	0.0	Hf1—C1—C5—C4	65.5 (4)
C21A—Hf1—C1—C6	−71.7 (9)	C2—C1—C5—C10	172.4 (5)
C11—Hf1—C1—C6	171.0 (5)	C6—C1—C5—C10	−4.0 (9)
C31—Hf1—C1—C6	46.4 (5)	Hf1—C1—C5—C10	−121.3 (5)
C21B—Hf1—C1—C6	−57.3 (8)	C2—C1—C5—Hf1	−66.3 (4)
C4—Hf1—C1—C6	−159.0 (6)	C6—C1—C5—Hf1	117.3 (6)
C5—Hf1—C1—C6	−122.1 (6)	Hf1—C1—C5—Hf1	0.000 (1)
C3—Hf1—C1—C6	160.0 (6)	C21A—Hf1—C5—C4	114.6 (7)
C2—Hf1—C1—C6	122.9 (7)	C11—Hf1—C5—C4	21.9 (4)
C5—C1—C2—C3	0.5 (6)	C31—Hf1—C5—C4	−129.2 (3)
C6—C1—C2—C3	176.9 (5)	C21B—Hf1—C5—C4	128.3 (7)
Hf1—C1—C2—C3	−65.6 (4)	C4—Hf1—C5—C4	0.000 (1)
C5—C1—C2—C7	−173.3 (6)	C3—Hf1—C5—C4	−37.5 (3)
C6—C1—C2—C7	3.1 (10)	C1—Hf1—C5—C4	−115.5 (4)
Hf1—C1—C2—C7	120.6 (6)	C2—Hf1—C5—C4	−78.2 (3)
C5—C1—C2—Hf1	66.1 (4)	C21A—Hf1—C5—C1	−130.0 (8)
C6—C1—C2—Hf1	−117.5 (6)	C11—Hf1—C5—C1	137.3 (3)
Hf1—C1—C2—Hf1	0.0	C31—Hf1—C5—C1	−13.7 (4)
C21A—Hf1—C2—C3	95.3 (10)	C21B—Hf1—C5—C1	−116.2 (7)
C11—Hf1—C2—C3	−33.8 (4)	C4—Hf1—C5—C1	115.5 (4)
C31—Hf1—C2—C3	−142.9 (4)	C3—Hf1—C5—C1	77.9 (3)
C21B—Hf1—C2—C3	114.8 (9)	C1—Hf1—C5—C1	0.000 (3)
C4—Hf1—C2—C3	37.4 (3)	C2—Hf1—C5—C1	37.3 (3)
C5—Hf1—C2—C3	77.9 (3)	C21A—Hf1—C5—C10	−7.4 (8)
C3—Hf1—C2—C3	0.000 (2)	C11—Hf1—C5—C10	−100.0 (5)
C1—Hf1—C2—C3	115.0 (5)	C31—Hf1—C5—C10	108.9 (5)
C21A—Hf1—C2—C1	−19.7 (10)	C21B—Hf1—C5—C10	6.4 (7)
C11—Hf1—C2—C1	−148.8 (3)	C4—Hf1—C5—C10	−121.9 (6)
C31—Hf1—C2—C1	102.1 (4)	C3—Hf1—C5—C10	−159.4 (6)
C21B—Hf1—C2—C1	−0.2 (10)	C1—Hf1—C5—C10	122.6 (6)
C4—Hf1—C2—C1	−77.6 (3)	C2—Hf1—C5—C10	159.9 (6)
C5—Hf1—C2—C1	−37.0 (3)	C21A—Hf1—C11—C12	111.2 (7)
C3—Hf1—C2—C1	−115.0 (5)	C31—Hf1—C11—C12	−11.2 (4)
C1—Hf1—C2—C1	0.0	C21B—Hf1—C11—C12	100.3 (7)
C21A—Hf1—C2—C7	−142.6 (11)	C4—Hf1—C11—C12	−154.0 (4)
C11—Hf1—C2—C7	88.2 (6)	C5—Hf1—C11—C12	−165.7 (3)
C31—Hf1—C2—C7	−20.9 (6)	C3—Hf1—C11—C12	−121.1 (4)
C21B—Hf1—C2—C7	−123.2 (10)	C1—Hf1—C11—C12	−130.1 (4)
C4—Hf1—C2—C7	159.5 (6)	C2—Hf1—C11—C12	−103.5 (4)
C5—Hf1—C2—C7	−160.0 (6)	Hf1—C11—C12—C17	−90.9 (5)
C3—Hf1—C2—C7	122.1 (7)	Hf1—C11—C12—C13	87.8 (5)
C1—Hf1—C2—C7	−122.9 (7)	C17—C12—C13—C14	−0.5 (8)
C1—C2—C3—C4	0.0 (6)	C11—C12—C13—C14	−179.3 (6)
C7—C2—C3—C4	173.9 (5)	C12—C13—C14—C15	−0.5 (10)
Hf1—C2—C3—C4	−65.6 (3)	C13—C14—C15—C16	0.8 (11)
C1—C2—C3—C8	−174.9 (5)	C14—C15—C16—C17	−0.2 (11)
C7—C2—C3—C8	−1.0 (9)	C15—C16—C17—C12	−0.8 (10)
Hf1—C2—C3—C8	119.5 (5)	C13—C12—C17—C16	1.1 (8)
C1—C2—C3—Hf1	65.6 (4)	C11—C12—C17—C16	179.9 (6)
C7—C2—C3—Hf1	−120.5 (6)	C11—Hf1—C21A—C22A	−53.2 (17)
Hf1—C2—C3—Hf1	0.000 (1)	C31—Hf1—C21A—C22A	63.7 (18)
C21A—Hf1—C3—C2	−113.4 (8)	C21B—Hf1—C21A—C22A	80 (3)
C11—Hf1—C3—C2	149.7 (3)	C4—Hf1—C21A—C22A	−144.3 (16)
C31—Hf1—C3—C2	39.5 (4)	C5—Hf1—C21A—C22A	−173.9 (17)
C21B—Hf1—C3—C2	−98.6 (8)	C3—Hf1—C21A—C22A	−145.1 (13)
C4—Hf1—C3—C2	−114.9 (5)	C1—Hf1—C21A—C22A	161.1 (15)
C5—Hf1—C3—C2	−77.7 (3)	C2—Hf1—C21A—C22A	171.8 (11)
C1—Hf1—C3—C2	−37.2 (3)	Hf1—C21A—C22A—C27A	−83 (4)
C2—Hf1—C3—C2	0.000 (3)	Hf1—C21A—C22A—C23A	97 (3)
C21A—Hf1—C3—C4	1.5 (8)	C27A—C22A—C23A—C24A	1 (2)
C11—Hf1—C3—C4	−95.4 (3)	C21A—C22A—C23A—C24A	−179 (4)
C31—Hf1—C3—C4	154.4 (3)	C22A—C23A—C24A—C25A	2 (2)
C21B—Hf1—C3—C4	16.3 (8)	C23A—C24A—C25A—C26A	−3 (4)
C4—Hf1—C3—C4	0.0	C24A—C25A—C26A—C27A	3 (4)
C5—Hf1—C3—C4	37.2 (3)	C23A—C22A—C27A—C26A	−1 (4)
C1—Hf1—C3—C4	77.7 (3)	C21A—C22A—C27A—C26A	178 (3)
C2—Hf1—C3—C4	114.9 (5)	C25A—C26A—C27A—C22A	−0 (4)
C21A—Hf1—C3—C8	124.0 (9)	C21A—Hf1—C21B—C22B	−76 (3)
C11—Hf1—C3—C8	27.1 (5)	C11—Hf1—C21B—C22B	−26.2 (13)
C31—Hf1—C3—C8	−83.1 (5)	C31—Hf1—C21B—C22B	89.8 (11)
C21B—Hf1—C3—C8	138.8 (9)	C4—Hf1—C21B—C22B	−121.3 (11)
C4—Hf1—C3—C8	122.5 (6)	C5—Hf1—C21B—C22B	−147.4 (12)
C5—Hf1—C3—C8	159.7 (5)	C3—Hf1—C21B—C22B	−130.4 (9)
C1—Hf1—C3—C8	−159.8 (5)	C1—Hf1—C21B—C22B	−176.8 (10)
C2—Hf1—C3—C8	−122.6 (6)	C2—Hf1—C21B—C22B	−176.7 (8)
C2—C3—C4—C5	−0.6 (6)	Hf1—C21B—C22B—C27B	−92 (3)
C8—C3—C4—C5	174.3 (5)	Hf1—C21B—C22B—C23B	86 (2)
Hf1—C3—C4—C5	−66.8 (4)	C27B—C22B—C23B—C24B	−1.0 (17)
C2—C3—C4—C9	−178.4 (5)	C21B—C22B—C23B—C24B	−179 (3)
C8—C3—C4—C9	−3.5 (9)	C22B—C23B—C24B—C25B	0 (2)
Hf1—C3—C4—C9	115.4 (5)	C23B—C24B—C25B—C26B	−1 (4)
C2—C3—C4—Hf1	66.3 (4)	C24B—C25B—C26B—C27B	2 (3)
C8—C3—C4—Hf1	−118.9 (5)	C23B—C22B—C27B—C26B	2 (3)
Hf1—C3—C4—Hf1	0.0	C21B—C22B—C27B—C26B	−180 (3)
C21A—Hf1—C4—C5	−64.1 (7)	C25B—C26B—C27B—C22B	−3 (3)
C11—Hf1—C4—C5	−161.5 (3)	C21A—Hf1—C31—C32	−21.2 (8)
C31—Hf1—C4—C5	77.1 (4)	C11—Hf1—C31—C32	88.5 (5)
C21B—Hf1—C4—C5	−53.9 (6)	C21B—Hf1—C31—C32	−25.2 (6)
C5—Hf1—C4—C5	0.000 (2)	C4—Hf1—C31—C32	−156.6 (4)
C3—Hf1—C4—C5	114.7 (4)	C5—Hf1—C31—C32	−117.6 (4)
C1—Hf1—C4—C5	36.9 (3)	C3—Hf1—C31—C32	−177.4 (4)
C2—Hf1—C4—C5	77.6 (3)	C1—Hf1—C31—C32	−124.9 (5)
C21A—Hf1—C4—C3	−178.8 (7)	C2—Hf1—C31—C32	−157.0 (5)
C11—Hf1—C4—C3	83.8 (3)	Hf1—C31—C32—C37	−89.6 (6)
C31—Hf1—C4—C3	−37.6 (4)	Hf1—C31—C32—C33	88.7 (6)
C21B—Hf1—C4—C3	−168.6 (6)	C37—C32—C33—C34	−1.5 (8)
C5—Hf1—C4—C3	−114.7 (4)	C31—C32—C33—C34	−179.9 (5)
C3—Hf1—C4—C3	0.000 (1)	C32—C33—C34—C35	0.7 (10)
C1—Hf1—C4—C3	−77.8 (3)	C33—C34—C35—C36	0.3 (11)
C2—Hf1—C4—C3	−37.1 (3)	C34—C35—C36—C37	−0.3 (10)
C21A—Hf1—C4—C9	58.3 (7)	C35—C36—C37—C32	−0.6 (9)
C11—Hf1—C4—C9	−39.1 (4)	C33—C32—C37—C36	1.5 (8)
C31—Hf1—C4—C9	−160.5 (4)	C31—C32—C37—C36	179.9 (5)
C21B—Hf1—C4—C9	68.5 (6)