A fluoro­phenylboron-functionalized zirconium silsesquioxane complex

Bis(η⁵-cyclo­penta­dienyl)[rel-(1R,5S,7R,14S)-(1,3,5,7,9,11,14-hepta­cyclo­pentyl-7,14-dioxidotri­cyclo­[7.3.3^1,9.1^5,11]­hepta­siloxan-3-yloxy)­bis­(penta­fluoro­phenyl)­borane(2−)]­zirconium, [Zr(C₅H₅)₂(C₄₇H₆₃BF₁₀O₁₂Si₇)], consists of [ZrCp₂] (Cp is cyclopentadienyl) and [(C₆F₅)₂B] moieties bound to a silsesquioxane core. The silsesquioxane binds to the Zr atom through two of its O atoms to form a distorted tetrahedron. The [(C₆F₅)₂B] moiety is bound to the silsesquioxane through an O atom, forming an Si—O—B bond angle of 168.4 (4)°. The steric and electronic effects of the Zr atom and the borate moieties force the silsesquioxane core to distort. These distortions can be seen by examination of the Si—O—Si bond angles.

S1. Comment

The use of organosilsesquioxanes as soluble models of the silanol sites on the surface of silica is well established, and this work is featured in a number of reviews (Feher & Budzichowski, 1995; Baney et al. 1995; Abbenhuis, 2000; Lorenz et al. 2000; Marciniec & Maciejewski, 2001; Duchateau, 2002). In particular, the use of such compounds to model the chemistry of surface-bound organometallic complexes involved in catalysis is a growing field of interest, and a number of cyclopentadienyl group 4 complexes featuring silsesquioxane ligands have been structurally characterized (Feher, 1986; Buys et al., 1994; Duchateau et al., 1998, 1999, 2000; Gun'ko et al., 1999; Wada et al., 2000; Edelmann et al., 2000, 2001; Severn et al., 2002, 2003).

In recent work, we reported the synthesis and structural characterization of tris(boryl)silsesquioxane, (I) (Metcalfe et al., 2002), a model compound for hydroxylated silica modified by reactive organoboranes (Tian et al., 1999), and investigated its reactivity towards a typical metallocene complex (Cp₂ZrMe₂) in solution by variable-temperature NMR spectroscopy. The principal product of this reaction was the title novel zirconocene-functionalized silsesquioxane, (II), which had resisted our earlier attempts to obtain it in crystalline form. We now report the molecular structure of complex (II), which features both zirconocene and Lewis acidic borane moieties within the same silsesquioxane molecule. This appears to be the first structurally characterized compound of this kind. \sch

A view of complex (II) is depicted in Fig. 1, and a plot of the silsesquioxane cage and the attached cyclopentyl rings is shown in Fig. 2. The silsesquioxane core refined without difficulty. Despite the low temperature used for data collection, the quality of the result was limited by the relatively poor quality of the crystals available, which scattered weakly beyond 2θ = 50°. The structural refinement of (I), precursor to (II), did not have the same refinement problems as compound (II).

The Zr atom is bound to two silsesquioxane O atoms and two cyclopentadiene rings in a distorted tetrahedral geometry. The two Zr—O bond lengths are equal within experimental error. The occupancies in the disordered cyclopentadiene ring were found to be 66% for the C6A—C10A ring and 34% for the C6B—C10B ring. Zr···centroid distances for the cyclopentadiene rings are 2.246 (6), 2.248 (11) and 2.213 (17) Å for rings C1—C5, C6A—C10A and C6B—C10B, respectively. The bond angles between the cyclopentadiene centroids and the Zr atom are 129.7 (3) and 127.9 (5)° for (C1—C5)—Zr-(C6A—C10A) and (C1—C5)—Zr-(C6B—C10B), respectively. The geometrical parameters associated with the zirconocene moiety are similar to those found in the related compound {[(C₅H₉)Si]₇O₆(O₂ZrCp₂)-(OSiMePh₂)}, recently reported and structurally characterized by Duchateau and co-workers (Skowronska-Ptasinska et al., 2001).

The silsesquioxane in (II) is also functionalized with a bis(perfluorophenyl)borane moiety. The geometrical parameters associated with this moiety are similar to those observed in the structure of (I), where the average B—O distance is 1.330 (1) Å, while the B—O—Si angles are 143.8 (1), 169.0 (1) and 170.7 (1)°. Although these B—O bonds are short, and the angles at O in general are obtuse, the extent of a π-type interaction between B and O remains to be proven. In particular, unlike the compound (C₆F₅)₂BOH, in which there is restricted rotation about the B—O bond in solution (Beringhelli et al., 2003), the ¹⁹F NMR spectra of either (I) or (II) are invariant over the temperature range 193–298 K in solution. That borinic acid is trimeric in the solid state, featuring trigonal-pyramidal O and tetrahedral B atoms, with long B—O distances of 1.526 (6) Å (Beringhelli et al., 2003), and so cannot be structurally compared with (I) or (II).

Despite the close proximity of the Lewis acidic borane moiety to the Zr—O groups in (II), there is no evidence of a dative interaction between B and either O1 or O2: these B—O distances are in excess of 6 Å. In fact, the only intra-molecular contacts which are within the van der Waals radii of the respective elements are those between B and the C9A—H10A bond of the endocyclic Cp ring, where the B—C10A distance is 3.78 (1) Å. While these contacts are suggestive of a weak dative interaction between the B atom and the π cloud of this Cp ring, the fact that the bond angles at B sum to 360.0 (5)° suggests that these close contacts do not really represent bonding interactions but are caused by structural constraints of the silsesquioxane cage.

The Si—O bond distances within the structure of (II) show considerable variation, ranging from 1.588 (4) to 1.629 (4) Å. As might be expected, the Si—O bond lengths associated with the cage respond to changes in those Si—O bonds associated with the two different exocyclic substituents. Thus, while the shortest Si—O distances in the structure are those associated with the zirconocene group, the average lengths of the remaining Si—O bonds about these Si atoms are significantly longer in comparison [Si1 1.622 (4) and Si2 1.624 (4) Å] and are, in fact, somewhat longer than the average length of the Si—O bonds associated with the non-peripheral Si atoms of the cage [1.615 (4) Å for atoms Si4 to Si7]. Similarly, the long exocyclic Si3—O3 bond involving the borane moiety is counter-balanced by the relatively short remaining Si—O lengths involving this Si atom [1.609 (4) Å].

The Si—O—Si angles in (II), which range from 145.2 (3) to 163.0 (3)°, reveal distortions of the silsesquioxane cage, due to the steric and electronic requirements of both the zirconocene and borane groups. This is evident from both the progressive increase in average Si—O—Si bond angles as one moves from the unique vertex Si atom [Si7 with 147.3 (3)°] outwards [Si4, Si5 and Si6 with 150.5 (3)°] to the edges [Si1, Si2 and Si3 with 152.0 (3)°] of the cage, where the variation in these last Si—O—Si angles is considerable [Si1 157.0 (3), Si2 151.0 (3) and Si3 148.2 (3)°].

S2. Experimental

The synthesis, isolation and characterization of compound (II) have been reported in detail elsewhere (Metcalfe et al., 2002). Single crystals of this compound suitable for X-ray analysis were obtained by slow cooling of a concentrated hexane-acetonitrile mixture in the ratio of 5:1 v:v. Initially, (II) was dissolved in a minimal quantity of hexane in a vial, and then acetonitrile was added dropwise into this hexane solution. The final solution separated into two phases which were slowly cooled to 243 K. Crystals of (II) grew at the interface, and after 3 d these began to separate and were isolated by decantation of the mother liquor.

S3. Refinement

Disorders were originally modeled without restraints. This produced unreasonable bond distances and angles for the 3,4-position of some cyclopentane rings. Distance restraints were thus applied to the 3,4-position of the disordered cyclopentane rings. Similarity restraints were applied to the various disordered cyclopentane rings and the disordered cyclopentadiene ring. Refining the anisotropic parameters of the disordered atoms yielded high U_iso values. Therefore, the disordered portions were refined isotropically. All H atoms were calculated and their positions refined based on a riding model. Bond lengths and angles for H atoms were idealized (cyclopentadiene C—H = 1.00 Å and secondary C—H = 0.99 Å) upon refinement. U_iso(H) values were fixed to 1.2U_eq(C). The occupancy of each disordered H atom was set according to the occupancy of its parent C atom.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (II), showing 50% probability displacement ellipsoids. Cyclopentadiene rings are shown with artificially low isotropic displacement parameters, and the cyclopentane rings have been omitted for clarity, except for the C atoms directly attached to the Si atoms, which are shown with artifically low isotropic displacement parameters.
	Fig. 2. The silsesquioxane cage of (II), with the cyclopentane rings, depicted at the 50% probability level. The cyclopentadiene rings and the fluorophenyl rings have been omitted for clarity. The cyclopentane rings are shown with artificially low isotropic displacement parameters.

Bis(η⁵-cyclopentadienyl)[rel-(1R,5S,7R,14S)-(1,3,5,7,9,11,14- heptacyclopentyl-7,14-dihydroxytricyclo[7.3.3.0^15,11]heptasiloxan-3- yl)bis(pentafluorophenyl)borinato(2-)]zirconium

Crystal data

[Zr(C5H5)2(C47H63BF10O12Si7)]	Z = 2
Mr = 1438.81	F(000) = 1488
Triclinic, P1	Dx = 1.497 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 11.0484 (17) Å	Cell parameters from 6719 reflections
b = 11.3415 (18) Å	θ = 2.4–27.3°
c = 25.919 (4) Å	µ = 0.39 mm^−1
α = 82.620 (3)°	T = 100 K
β = 86.414 (3)°	Plate, colorless
γ = 82.697 (3)°	0.20 × 0.10 × 0.05 mm
V = 3191.2 (9) Å^3

Data collection

Bruker Apex CCD area-detector diffractometer	6812 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.092
Graphite monochromator	θmax = 25.0°, θmin = 0.8°
ϕ and ω scans	h = −13→12
20985 measured reflections	k = −13→13
11091 independent reflections	l = −30→30

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.069	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.160	H-atom parameters constrained
S = 0.93	w = 1/[σ^2(Fo^2) + (0.0618P)^2] where P = (Fo^2 + 2Fc^2)/3
11091 reflections	(Δ/σ)max = 0.004
780 parameters	Δρmax = 1.22 e Å^−3
226 restraints	Δρmin = −0.44 e Å^−3

Special details

Experimental. An absorption correction was originally applied to the data. However, better results were achieved by using the uncorrected data.

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.

Disordered atoms were refined isotropically. Attempts to refine these atoms anisotropically lead to unreasonable U values.

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

	x	y	z	Uiso*/Ueq	Occ. (<1)
Zr	0.31339 (5)	0.96024 (5)	0.66048 (2)	0.02733 (18)
Si1	0.61660 (14)	1.00626 (13)	0.67096 (6)	0.0221 (4)
Si2	0.47031 (14)	0.67734 (13)	0.65214 (6)	0.0230 (4)
Si3	0.56896 (14)	0.75043 (13)	0.85126 (6)	0.0222 (4)
Si4	0.71677 (14)	0.77433 (14)	0.62088 (6)	0.0228 (4)
Si5	0.74279 (14)	0.89382 (13)	0.77628 (6)	0.0209 (4)
Si6	0.57093 (14)	0.58602 (13)	0.76364 (6)	0.0210 (4)
Si7	0.82578 (14)	0.66166 (13)	0.72598 (6)	0.0220 (4)
F12	0.2716 (3)	0.6640 (3)	0.86607 (13)	0.0439 (9)
F13	0.0857 (3)	0.5521 (3)	0.90769 (14)	0.0465 (10)
F14	−0.0527 (3)	0.6337 (3)	0.98898 (14)	0.0495 (10)
F15	0.0001 (3)	0.8284 (3)	1.02922 (13)	0.0478 (10)
F16	0.1876 (3)	0.9409 (3)	0.98921 (12)	0.0372 (9)
F18	0.1662 (3)	1.0774 (3)	0.88195 (13)	0.0408 (9)
F19	0.1823 (4)	1.2991 (3)	0.90436 (15)	0.0558 (11)
F20	0.3844 (4)	1.3481 (4)	0.94693 (17)	0.0756 (14)
F21	0.5746 (4)	1.1740 (4)	0.96482 (18)	0.0780 (14)
F22	0.5626 (3)	0.9530 (3)	0.94123 (15)	0.0520 (10)
O1	0.4715 (3)	1.0132 (3)	0.67402 (15)	0.0295 (10)
O2	0.3750 (3)	0.7950 (3)	0.64700 (15)	0.0304 (10)
O3	0.4417 (4)	0.8133 (4)	0.87585 (15)	0.0365 (11)
O4	0.4931 (3)	0.6372 (3)	0.71351 (14)	0.0275 (9)
O5	0.5304 (3)	0.6729 (3)	0.80822 (14)	0.0259 (9)
O6	0.6457 (4)	0.8535 (3)	0.82311 (14)	0.0294 (10)
O7	0.6673 (3)	0.9639 (3)	0.72846 (14)	0.0320 (10)
O8	0.6753 (4)	0.9098 (3)	0.63222 (14)	0.0332 (10)
O9	0.5996 (4)	0.7027 (4)	0.62214 (15)	0.0360 (10)
O10	0.8067 (3)	0.7091 (3)	0.66554 (14)	0.0314 (10)
O11	0.8240 (3)	0.7750 (3)	0.75850 (14)	0.0300 (10)
O12	0.7151 (3)	0.5866 (3)	0.74924 (14)	0.0286 (10)
C1	0.3153 (7)	1.1351 (6)	0.5887 (3)	0.058 (2)
H1A	0.3612	1.2055	0.5889	0.069*
C2	0.1936 (7)	1.1309 (6)	0.6049 (3)	0.059 (2)
H2A	0.1369	1.1976	0.6180	0.071*
C3	0.1600 (7)	1.0245 (7)	0.5905 (3)	0.067 (2)
H3A	0.0750	1.0024	0.5917	0.080*
C4	0.2613 (9)	0.9674 (7)	0.5656 (3)	0.067 (2)
H4A	0.2612	0.8959	0.5467	0.081*
C5	0.3576 (8)	1.0323 (8)	0.5657 (3)	0.065 (2)
H5A	0.4379	1.0176	0.5461	0.078*
C6A	0.2125 (11)	1.0551 (9)	0.7383 (4)	0.043 (3)*	0.657 (15)
H6A	0.2087	1.1415	0.7432	0.052*	0.657 (15)
C7A	0.1218 (10)	1.0035 (12)	0.7175 (4)	0.049 (4)*	0.657 (15)
H7A	0.0419	1.0462	0.7053	0.058*	0.657 (15)
C8A	0.1538 (12)	0.8793 (11)	0.7246 (5)	0.050 (3)*	0.657 (15)
H8A	0.0999	0.8187	0.7181	0.060*	0.657 (15)
C9A	0.2626 (12)	0.8538 (9)	0.7509 (5)	0.043 (3)*	0.657 (15)
H9A	0.2999	0.7726	0.7659	0.051*	0.657 (15)
C10A	0.2994 (8)	0.9626 (12)	0.7593 (4)	0.038 (3)*	0.657 (15)
H10A	0.3680	0.9726	0.7811	0.045*	0.657 (15)
C6B	0.210 (2)	0.8341 (10)	0.7341 (7)	0.040 (6)*	0.343 (15)
H6B	0.2118	0.7450	0.7379	0.048*	0.343 (15)
C7B	0.1187 (14)	0.9172 (19)	0.7108 (7)	0.050 (6)*	0.343 (15)
H7B	0.0437	0.8975	0.6956	0.060*	0.343 (15)
C8B	0.1409 (18)	1.0317 (13)	0.7195 (7)	0.047 (8)*	0.343 (15)
H8B	0.0836	1.1069	0.7123	0.057*	0.343 (15)
C9B	0.2458 (18)	1.0193 (17)	0.7483 (7)	0.048 (6)*	0.343 (15)
H9B	0.2761	1.0843	0.7648	0.058*	0.343 (15)
C10B	0.2885 (13)	0.897 (2)	0.7573 (6)	0.034 (6)*	0.343 (15)
H10B	0.3555	0.8607	0.7807	0.041*	0.343 (15)
C11	0.2411 (5)	0.8088 (5)	0.9253 (2)	0.0232 (13)
C12	0.2076 (5)	0.7080 (5)	0.9066 (2)	0.0261 (14)
C13	0.1123 (6)	0.6490 (5)	0.9273 (2)	0.0299 (14)
C14	0.0421 (5)	0.6890 (6)	0.9685 (2)	0.0323 (15)
C15	0.0692 (5)	0.7885 (5)	0.9888 (2)	0.0291 (14)
C16	0.1651 (5)	0.8449 (5)	0.9674 (2)	0.0261 (14)
C17	0.3635 (5)	1.0068 (5)	0.9109 (2)	0.0261 (14)
C18	0.2689 (6)	1.0986 (5)	0.9024 (2)	0.0303 (14)
C19	0.2746 (6)	1.2119 (5)	0.9143 (2)	0.0409 (17)
C20	0.3785 (7)	1.2385 (6)	0.9347 (3)	0.0450 (18)
C21	0.4743 (6)	1.1495 (6)	0.9437 (3)	0.0451 (18)
C22	0.4670 (6)	1.0377 (6)	0.9310 (2)	0.0388 (16)
C23	0.6675 (5)	1.1517 (5)	0.6450 (2)	0.0335 (15)
H23A	0.6195	1.2142	0.6644	0.040*
C24	0.8026 (6)	1.1609 (6)	0.6502 (3)	0.053 (2)
H24A	0.8144	1.1895	0.6839	0.064*
H24B	0.8502	1.0810	0.6496	0.064*
C25A	0.8471 (15)	1.247 (3)	0.6060 (9)	0.057 (6)*	0.50 (6)
H25A	0.9114	1.2055	0.5841	0.068*	0.50 (6)
H25B	0.8804	1.3135	0.6193	0.068*	0.50 (6)
C26	0.7329 (7)	1.2932 (7)	0.5749 (3)	0.073 (3)
H26A	0.6910	1.3681	0.5866	0.088*
H26B	0.7543	1.3077	0.5371	0.088*
C27	0.6550 (7)	1.1928 (7)	0.5867 (3)	0.066 (2)
H27A	0.6845	1.1266	0.5659	0.079*
H27B	0.5688	1.2213	0.5790	0.079*
C25B	0.821 (3)	1.281 (2)	0.6168 (9)	0.059 (6)*	0.50 (6)
H25C	0.8032	1.3488	0.6380	0.071*	0.50 (6)
H25D	0.9057	1.2802	0.6020	0.071*	0.50 (6)
C28	0.4126 (5)	0.5551 (5)	0.6237 (2)	0.0296 (14)
H28A	0.4677	0.4796	0.6335	0.035*
C29	0.4063 (7)	0.5735 (6)	0.5643 (2)	0.0470 (19)
H29A	0.3729	0.6568	0.5519	0.056*
H29B	0.4882	0.5558	0.5473	0.056*
C30	0.3212 (8)	0.4854 (6)	0.5528 (3)	0.058 (2)
H30A	0.2744	0.5173	0.5217	0.070*
H30B	0.3681	0.4076	0.5468	0.070*
C31	0.2372 (8)	0.4709 (8)	0.6003 (3)	0.082 (3)
H31A	0.1531	0.5064	0.5919	0.098*
H31B	0.2358	0.3849	0.6128	0.098*
C32	0.2828 (7)	0.5331 (7)	0.6414 (3)	0.054 (2)
H32A	0.2819	0.4823	0.6755	0.065*
H32B	0.2311	0.6099	0.6449	0.065*
C33	0.6510 (5)	0.6558 (5)	0.9037 (2)	0.0306 (15)
H33A	0.6692	0.7090	0.9295	0.037*
C34	0.5804 (6)	0.5577 (6)	0.9332 (2)	0.0413 (17)
H34A	0.5247	0.5897	0.9609	0.050*
H34B	0.5323	0.5231	0.9092	0.050*
C35	0.6808 (7)	0.4649 (7)	0.9564 (3)	0.077 (3)
H35A	0.7035	0.4855	0.9902	0.093*
H35B	0.6529	0.3845	0.9620	0.093*
C36	0.7843 (7)	0.4665 (6)	0.9190 (3)	0.064 (2)
H36A	0.7845	0.4022	0.8965	0.077*
H36B	0.8617	0.4532	0.9374	0.077*
C37	0.7731 (6)	0.5875 (6)	0.8863 (2)	0.0434 (18)
H37A	0.7735	0.5779	0.8488	0.052*
H37B	0.8420	0.6316	0.8919	0.052*
C38	0.8025 (5)	0.7719 (5)	0.5586 (2)	0.0285 (14)
H38A	0.7462	0.8058	0.5301	0.034*
C39	0.9110 (6)	0.8451 (6)	0.5545 (3)	0.0457 (18)
H39A	0.8869	0.9268	0.5369	0.055*
H39B	0.9372	0.8519	0.5897	0.055*
C40	1.0142 (7)	0.7829 (7)	0.5236 (4)	0.077 (3)
H40A	1.0867	0.7595	0.5449	0.093*
H40B	1.0372	0.8359	0.4921	0.093*
C41	0.9652 (7)	0.6712 (7)	0.5086 (3)	0.064 (2)
H41A	0.9357	0.6867	0.4727	0.077*
H41B	1.0300	0.6021	0.5104	0.077*
C42	0.8636 (6)	0.6469 (5)	0.5467 (2)	0.0409 (17)
H42A	0.8947	0.5986	0.5788	0.049*
H42B	0.8047	0.6031	0.5319	0.049*
C43	0.8415 (5)	0.9878 (5)	0.8018 (2)	0.0268 (14)
H43A	0.8967	1.0185	0.7724	0.032*
C44	0.7722 (6)	1.0969 (5)	0.8255 (2)	0.0383 (17)
H44A	0.7705	1.1700	0.8000	0.046*
H44B	0.6871	1.0827	0.8362	0.046*
C45	0.8424 (6)	1.1095 (6)	0.8721 (2)	0.0466 (19)
H45A	0.9133	1.1540	0.8616	0.056*
H45B	0.7896	1.1514	0.8980	0.056*
C46	0.8835 (6)	0.9818 (6)	0.8937 (2)	0.0450 (18)
H46A	0.8158	0.9446	0.9135	0.054*
H46B	0.9525	0.9776	0.9167	0.054*
C47	0.9228 (6)	0.9207 (5)	0.8456 (2)	0.0371 (16)
H47A	0.9101	0.8351	0.8518	0.045*
H47B	1.0102	0.9265	0.8362	0.045*
C48	0.5371 (5)	0.4338 (5)	0.7870 (2)	0.0297 (14)
H48A	0.5871	0.4034	0.8178	0.036*
C49	0.5666 (6)	0.3453 (5)	0.7465 (3)	0.0400 (17)
H49A	0.5625	0.3880	0.7107	0.048*
H49B	0.6494	0.3014	0.7508	0.048*
C50	0.4714 (7)	0.2608 (7)	0.7564 (4)	0.085 (3)
H50A	0.4516	0.2357	0.7230	0.102*
H50B	0.5039	0.1883	0.7792	0.102*
C51A	0.3595 (12)	0.3185 (14)	0.7814 (8)	0.049 (5)*	0.49 (3)
H51A	0.3257	0.2625	0.8095	0.058*	0.49 (3)
H51B	0.2964	0.3468	0.7557	0.058*	0.49 (3)
C52	0.4026 (7)	0.4234 (6)	0.8034 (3)	0.054 (2)
H52A	0.3930	0.4117	0.8419	0.064*
H52B	0.3517	0.4984	0.7906	0.064*
C51B	0.4036 (15)	0.2845 (10)	0.8026 (6)	0.040 (5)*	0.51 (3)
H51C	0.4432	0.2387	0.8335	0.048*	0.51 (3)
H51D	0.3195	0.2634	0.8020	0.048*	0.51 (3)
C53	0.9721 (5)	0.5641 (5)	0.7300 (2)	0.0302 (14)
H53A	1.0353	0.6092	0.7097	0.036*
C54	0.9672 (7)	0.4498 (6)	0.7044 (3)	0.060 (2)
H54A	0.8815	0.4364	0.7007	0.072*
H54B	1.0094	0.4557	0.6695	0.072*
C55A	1.0298 (15)	0.3515 (10)	0.7397 (4)	0.096 (5)*	0.745 (19)
H55A	1.1194	0.3439	0.7329	0.115*	0.745 (19)
H55B	1.0000	0.2741	0.7367	0.115*	0.745 (19)
C56A	0.9933 (15)	0.3935 (10)	0.7938 (4)	0.094 (5)*	0.745 (19)
H56A	0.9058	0.3879	0.8034	0.113*	0.745 (19)
H56B	1.0438	0.3467	0.8214	0.113*	0.745 (19)
C57	1.0197 (7)	0.5220 (7)	0.7843 (3)	0.075 (3)
H57A	1.1083	0.5273	0.7848	0.090*
H57B	0.9758	0.5697	0.8106	0.090*
C55B	0.965 (3)	0.3535 (19)	0.7520 (10)	0.082 (11)*	0.255 (19)
H55C	0.8861	0.3598	0.7721	0.098*	0.255 (19)
H55D	0.9855	0.2715	0.7422	0.098*	0.255 (19)
C56B	1.068 (3)	0.3916 (16)	0.7812 (13)	0.098 (12)*	0.255 (19)
H56C	1.0763	0.3456	0.8162	0.118*	0.255 (19)
H56D	1.1473	0.3831	0.7612	0.118*	0.255 (19)
B	0.3522 (6)	0.8731 (6)	0.9022 (2)	0.0249 (16)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr	0.0195 (3)	0.0239 (3)	0.0374 (4)	−0.0005 (2)	−0.0059 (3)	0.0011 (3)
Si1	0.0221 (9)	0.0217 (8)	0.0223 (9)	−0.0018 (7)	−0.0029 (7)	−0.0011 (7)
Si2	0.0240 (9)	0.0252 (9)	0.0211 (9)	−0.0051 (7)	−0.0041 (7)	−0.0037 (7)
Si3	0.0217 (9)	0.0264 (9)	0.0190 (9)	−0.0059 (7)	0.0023 (7)	−0.0036 (7)
Si4	0.0236 (9)	0.0275 (9)	0.0176 (8)	−0.0037 (7)	0.0000 (7)	−0.0040 (7)
Si5	0.0210 (9)	0.0246 (8)	0.0182 (8)	−0.0060 (7)	−0.0015 (7)	−0.0038 (6)
Si6	0.0206 (9)	0.0230 (8)	0.0200 (9)	−0.0050 (7)	−0.0007 (7)	−0.0027 (7)
Si7	0.0199 (9)	0.0260 (9)	0.0196 (9)	−0.0004 (7)	−0.0023 (7)	−0.0029 (7)
F12	0.047 (2)	0.047 (2)	0.042 (2)	−0.0102 (18)	0.0152 (18)	−0.0246 (18)
F13	0.050 (2)	0.043 (2)	0.052 (2)	−0.0184 (18)	0.0008 (19)	−0.0163 (19)
F14	0.038 (2)	0.065 (3)	0.048 (2)	−0.027 (2)	0.0075 (19)	−0.001 (2)
F15	0.043 (2)	0.065 (3)	0.036 (2)	−0.0109 (19)	0.0200 (18)	−0.0151 (19)
F16	0.044 (2)	0.037 (2)	0.035 (2)	−0.0126 (17)	0.0103 (17)	−0.0185 (16)
F18	0.031 (2)	0.041 (2)	0.050 (2)	−0.0014 (16)	−0.0087 (18)	−0.0036 (17)
F19	0.064 (3)	0.030 (2)	0.068 (3)	0.0015 (19)	0.011 (2)	0.0001 (19)
F20	0.105 (4)	0.047 (3)	0.084 (3)	−0.033 (2)	−0.003 (3)	−0.021 (2)
F21	0.077 (3)	0.077 (3)	0.094 (4)	−0.043 (3)	−0.030 (3)	−0.014 (3)
F22	0.036 (2)	0.058 (3)	0.063 (3)	−0.0106 (19)	−0.017 (2)	−0.003 (2)
O1	0.021 (2)	0.028 (2)	0.039 (2)	−0.0055 (17)	−0.0039 (19)	0.0001 (18)
O2	0.025 (2)	0.028 (2)	0.039 (3)	−0.0033 (18)	−0.0078 (19)	−0.0029 (18)
O3	0.032 (3)	0.051 (3)	0.028 (2)	−0.003 (2)	0.000 (2)	−0.014 (2)
O4	0.029 (2)	0.027 (2)	0.027 (2)	−0.0017 (17)	−0.0074 (18)	−0.0051 (17)
O5	0.022 (2)	0.034 (2)	0.024 (2)	−0.0081 (17)	0.0012 (17)	−0.0092 (17)
O6	0.036 (3)	0.027 (2)	0.027 (2)	−0.0064 (18)	−0.0004 (19)	−0.0075 (17)
O7	0.030 (2)	0.039 (2)	0.027 (2)	−0.0010 (19)	−0.0071 (19)	−0.0042 (18)
O8	0.041 (3)	0.032 (2)	0.025 (2)	0.0043 (19)	−0.003 (2)	−0.0056 (18)
O9	0.038 (3)	0.045 (3)	0.028 (2)	−0.012 (2)	0.005 (2)	−0.0121 (19)
O10	0.029 (2)	0.038 (2)	0.025 (2)	0.0022 (19)	0.0015 (18)	−0.0035 (18)
O11	0.024 (2)	0.033 (2)	0.036 (2)	−0.0055 (18)	−0.0039 (19)	−0.0134 (19)
O12	0.031 (2)	0.028 (2)	0.025 (2)	−0.0019 (18)	−0.0002 (18)	−0.0025 (17)
C1	0.057 (5)	0.042 (4)	0.069 (5)	−0.015 (3)	−0.029 (4)	0.033 (3)
C2	0.044 (4)	0.035 (4)	0.093 (6)	0.007 (3)	−0.032 (4)	0.010 (4)
C3	0.055 (5)	0.051 (4)	0.094 (6)	−0.008 (4)	−0.049 (4)	0.020 (4)
C4	0.094 (6)	0.052 (5)	0.059 (5)	0.004 (4)	−0.051 (5)	−0.005 (4)
C5	0.065 (5)	0.081 (6)	0.037 (4)	0.005 (4)	−0.011 (4)	0.023 (4)
C11	0.026 (3)	0.021 (3)	0.022 (3)	−0.001 (2)	−0.002 (3)	−0.001 (2)
C12	0.023 (3)	0.030 (3)	0.024 (3)	0.003 (3)	0.005 (3)	−0.005 (3)
C13	0.034 (4)	0.028 (3)	0.030 (4)	−0.005 (3)	−0.007 (3)	−0.006 (3)
C14	0.025 (4)	0.044 (4)	0.026 (4)	−0.005 (3)	−0.002 (3)	0.004 (3)
C15	0.024 (4)	0.037 (4)	0.025 (3)	0.001 (3)	0.005 (3)	−0.004 (3)
C16	0.028 (4)	0.026 (3)	0.024 (3)	0.000 (3)	−0.002 (3)	−0.004 (3)
C17	0.027 (3)	0.034 (3)	0.020 (3)	−0.012 (3)	0.000 (3)	−0.003 (3)
C18	0.032 (4)	0.036 (4)	0.024 (3)	−0.015 (3)	0.006 (3)	0.000 (3)
C19	0.050 (5)	0.028 (4)	0.041 (4)	0.001 (3)	0.009 (3)	−0.001 (3)
C20	0.068 (5)	0.031 (4)	0.040 (4)	−0.021 (4)	0.005 (4)	−0.007 (3)
C21	0.049 (5)	0.052 (5)	0.041 (4)	−0.030 (4)	−0.009 (4)	−0.004 (3)
C22	0.038 (4)	0.041 (4)	0.041 (4)	−0.014 (3)	0.000 (3)	−0.005 (3)
C23	0.037 (4)	0.023 (3)	0.040 (4)	−0.005 (3)	0.013 (3)	−0.007 (3)
C24	0.058 (5)	0.060 (5)	0.047 (4)	−0.034 (4)	−0.005 (4)	0.003 (3)
C26	0.065 (6)	0.063 (5)	0.079 (6)	−0.014 (4)	0.024 (5)	0.031 (4)
C27	0.047 (5)	0.075 (6)	0.066 (5)	−0.017 (4)	−0.016 (4)	0.044 (4)
C28	0.035 (4)	0.030 (3)	0.024 (3)	−0.001 (3)	−0.008 (3)	−0.005 (3)
C29	0.076 (6)	0.047 (4)	0.021 (4)	−0.018 (4)	−0.009 (4)	−0.004 (3)
C30	0.099 (7)	0.055 (5)	0.030 (4)	−0.034 (4)	−0.024 (4)	−0.003 (3)
C31	0.074 (7)	0.096 (7)	0.089 (7)	−0.036 (5)	−0.016 (6)	−0.034 (6)
C32	0.054 (5)	0.062 (5)	0.054 (5)	−0.034 (4)	−0.001 (4)	−0.010 (4)
C33	0.032 (4)	0.035 (4)	0.027 (3)	−0.013 (3)	−0.006 (3)	0.000 (3)
C34	0.045 (4)	0.050 (4)	0.026 (4)	−0.013 (3)	0.010 (3)	0.011 (3)
C35	0.076 (6)	0.058 (5)	0.078 (6)	0.013 (5)	0.017 (5)	0.034 (4)
C36	0.060 (6)	0.047 (5)	0.078 (6)	−0.004 (4)	0.004 (5)	0.014 (4)
C37	0.033 (4)	0.061 (5)	0.031 (4)	−0.006 (3)	−0.006 (3)	0.016 (3)
C38	0.026 (3)	0.040 (4)	0.021 (3)	−0.006 (3)	−0.002 (3)	−0.004 (3)
C39	0.058 (5)	0.047 (4)	0.036 (4)	−0.024 (4)	0.016 (3)	−0.012 (3)
C40	0.047 (5)	0.071 (6)	0.117 (8)	−0.021 (4)	0.017 (5)	−0.021 (5)
C41	0.059 (5)	0.052 (5)	0.080 (6)	−0.006 (4)	0.019 (5)	−0.016 (4)
C42	0.051 (5)	0.043 (4)	0.032 (4)	−0.017 (3)	0.020 (3)	−0.016 (3)
C43	0.028 (3)	0.025 (3)	0.029 (3)	−0.009 (3)	−0.003 (3)	−0.004 (3)
C44	0.043 (4)	0.022 (3)	0.053 (4)	−0.003 (3)	−0.019 (3)	−0.009 (3)
C45	0.054 (5)	0.046 (4)	0.044 (4)	0.004 (3)	−0.015 (4)	−0.023 (3)
C46	0.054 (5)	0.054 (4)	0.028 (4)	−0.004 (4)	−0.013 (3)	−0.006 (3)
C47	0.034 (4)	0.036 (4)	0.044 (4)	−0.003 (3)	−0.017 (3)	−0.007 (3)
C48	0.035 (4)	0.028 (3)	0.027 (3)	−0.010 (3)	−0.002 (3)	0.000 (3)
C49	0.039 (4)	0.021 (3)	0.060 (5)	−0.002 (3)	−0.008 (3)	−0.007 (3)
C50	0.065 (6)	0.056 (5)	0.145 (9)	−0.020 (4)	0.014 (6)	−0.048 (5)
C52	0.071 (5)	0.041 (4)	0.051 (5)	−0.025 (4)	0.029 (4)	−0.010 (3)
C53	0.022 (3)	0.032 (3)	0.033 (4)	0.001 (3)	0.002 (3)	0.003 (3)
C54	0.043 (5)	0.050 (5)	0.088 (6)	0.011 (4)	−0.001 (4)	−0.028 (4)
C57	0.057 (5)	0.105 (7)	0.055 (5)	0.038 (5)	−0.016 (4)	−0.019 (5)
B	0.029 (4)	0.037 (4)	0.011 (3)	−0.002 (3)	−0.006 (3)	−0.010 (3)

Geometric parameters (Å, º)

Zr—O1	1.983 (4)	C25A—C26	1.539 (12)
Zr—O2	1.978 (4)	C25A—H25A	0.9900
Zr—C1	2.540 (6)	C25A—H25B	0.9900
Zr—C2	2.539 (6)	C26—C25B	1.485 (11)
Zr—C3	2.534 (6)	C26—C27	1.503 (9)
Zr—C4	2.548 (7)	C26—H26A	0.9900
Zr—C5	2.527 (7)	C26—H26B	0.9900
Zr—C6A	2.538 (11)	C27—H27A	0.9900
Zr—C7A	2.537 (12)	C27—H27B	0.9900
Zr—C8A	2.523 (12)	C25B—H25C	0.9900
Zr—C9A	2.559 (11)	C25B—H25D	0.9900
Zr—C10A	2.559 (9)	C28—C32	1.520 (9)
Zr—C6B	2.537 (16)	C28—C29	1.531 (7)
Zr—C7B	2.513 (18)	C28—H28A	1.0000
Zr—C8B	2.489 (19)	C29—C30	1.524 (9)
Zr—C9B	2.498 (17)	C29—H29A	0.9900
Zr—C10B	2.528 (15)	C29—H29B	0.9900
Si1—O1	1.593 (4)	C30—C31	1.499 (11)
Si1—O7	1.618 (4)	C30—H30A	0.9900
Si1—O8	1.626 (4)	C30—H30B	0.9900
Si1—C23	1.842 (6)	C31—C32	1.496 (9)
Si2—O2	1.588 (4)	C31—H31A	0.9900
Si2—O9	1.623 (4)	C31—H31B	0.9900
Si2—O4	1.624 (4)	C32—H32A	0.9900
Si2—C28	1.849 (6)	C32—H32B	0.9900
Si3—O6	1.604 (4)	C33—C34	1.536 (8)
Si3—O5	1.614 (4)	C33—C37	1.540 (8)
Si3—O3	1.625 (4)	C33—H33A	1.0000
Si3—C33	1.831 (5)	C34—C35	1.525 (9)
Si4—O8	1.606 (4)	C34—H34A	0.9900
Si4—O9	1.610 (4)	C34—H34B	0.9900
Si4—O10	1.616 (4)	C35—C36	1.453 (9)
Si4—C38	1.822 (6)	C35—H35A	0.9900
Si5—O7	1.604 (4)	C35—H35B	0.9900
Si5—O11	1.623 (4)	C36—C37	1.512 (9)
Si5—O6	1.629 (4)	C36—H36A	0.9900
Si5—C43	1.825 (6)	C36—H36B	0.9900
Si6—O4	1.607 (4)	C37—H37A	0.9900
Si6—O12	1.614 (4)	C37—H37B	0.9900
Si6—O5	1.619 (4)	C38—C39	1.534 (8)
Si6—C48	1.831 (6)	C38—C42	1.550 (8)
Si7—O10	1.607 (4)	C38—H38A	1.0000
Si7—O12	1.620 (4)	C39—C40	1.504 (9)
Si7—O11	1.622 (4)	C39—H39A	0.9900
Si7—C53	1.840 (5)	C39—H39B	0.9900
F12—C12	1.343 (6)	C40—C41	1.543 (10)
F13—C13	1.341 (6)	C40—H40A	0.9900
F14—C14	1.335 (7)	C40—H40B	0.9900
F15—C15	1.349 (6)	C41—C42	1.477 (9)
F16—C16	1.346 (6)	C41—H41A	0.9900
F18—C18	1.344 (7)	C41—H41B	0.9900
F19—C19	1.340 (7)	C42—H42A	0.9900
F20—C20	1.331 (7)	C42—H42B	0.9900
F21—C21	1.340 (7)	C43—C44	1.546 (7)
F22—C22	1.349 (7)	C43—C47	1.552 (7)
O3—B	1.330 (7)	C43—H43A	1.0000
C1—C2	1.388 (10)	C44—C45	1.507 (8)
C1—C5	1.393 (10)	C44—H44A	0.9900
C1—H1A	1.0000	C44—H44B	0.9900
C2—C3	1.407 (9)	C45—C46	1.507 (8)
C2—H2A	1.0000	C45—H45A	0.9900
C3—C4	1.385 (11)	C45—H45B	0.9900
C3—H3A	1.0000	C46—C47	1.515 (8)
C4—C5	1.369 (11)	C46—H46A	0.9900
C4—H4A	1.0000	C46—H46B	0.9900
C5—H5A	1.0000	C47—H47A	0.9900
C6A—C7A	1.391 (12)	C47—H47B	0.9900
C6A—C10A	1.407 (12)	C48—C52	1.535 (8)
C6A—H6A	1.0000	C48—C49	1.537 (7)
C7A—C8A	1.400 (11)	C48—H48A	1.0000
C7A—H7A	1.0000	C49—C50	1.499 (8)
C8A—C9A	1.400 (12)	C49—H49A	0.9900
C8A—H8A	1.0000	C49—H49B	0.9900
C9A—C10A	1.393 (11)	C50—C51B	1.411 (10)
C9A—H9A	1.0000	C50—C51A	1.477 (11)
C10A—H10A	1.0000	C50—H50A	0.9900
C6B—C10B	1.400 (6)	C50—H50B	0.9900
C6B—C7B	1.400 (6)	C51A—C52	1.522 (11)
C6B—H6B	1.0000	C51A—H51A	0.9900
C7B—C8B	1.400 (6)	C51A—H51B	0.9900
C7B—H7B	1.0000	C52—C51B	1.576 (11)
C8B—C9B	1.400 (6)	C52—H52A	0.9900
C8B—H8B	1.0000	C52—H52B	0.9900
C9B—C10B	1.400 (6)	C51B—H51C	0.9900
C9B—H9B	1.0000	C51B—H51D	0.9900
C10B—H10B	1.0000	C53—C57	1.530 (8)
C11—C12	1.397 (8)	C53—C54	1.538 (8)
C11—C16	1.405 (7)	C53—H53A	1.0000
C11—B	1.555 (9)	C54—C55A	1.476 (11)
C12—C13	1.365 (8)	C54—C55B	1.540 (16)
C13—C14	1.369 (8)	C54—H54A	0.9900
C14—C15	1.378 (8)	C54—H54B	0.9900
C15—C16	1.359 (8)	C55A—C56A	1.551 (12)
C17—C18	1.385 (8)	C55A—H55A	0.9900
C17—C22	1.388 (8)	C55A—H55B	0.9900
C17—B	1.582 (8)	C56A—C57	1.509 (11)
C18—C19	1.369 (8)	C56A—H56A	0.9900
C19—C20	1.375 (9)	C56A—H56B	0.9900
C20—C21	1.376 (9)	C57—C56B	1.517 (16)
C21—C22	1.363 (8)	C57—H57A	0.9900
C23—C24	1.525 (8)	C57—H57B	0.9900
C23—C27	1.532 (8)	C55B—C56B	1.535 (15)
C23—H23A	1.0000	C55B—H55C	0.9900
C24—C25A	1.507 (12)	C55B—H55D	0.9900
C24—C25B	1.551 (13)	C56B—H56C	0.9900
C24—H24A	0.9900	C56B—H56D	0.9900
C24—H24B	0.9900
O2—Zr—O1	98.16 (15)	C18—C17—C22	115.5 (5)
O1—Zr—C1	81.3 (2)	C18—C17—B	122.7 (5)
O2—Zr—C1	121.3 (2)	C22—C17—B	121.6 (5)
O1—Zr—C2	107.8 (2)	F18—C18—C19	117.6 (5)
O2—Zr—C2	131.3 (2)	F18—C18—C17	119.6 (5)
O1—Zr—C3	133.6 (2)	C19—C18—C17	122.8 (6)
O2—Zr—C3	102.2 (2)	F19—C19—C18	120.9 (6)
O1—Zr—C4	117.2 (3)	F19—C19—C20	119.2 (6)
O2—Zr—C4	79.1 (2)	C18—C19—C20	119.8 (6)
O1—Zr—C5	86.7 (2)	F20—C20—C19	120.2 (6)
O2—Zr—C5	89.4 (2)	F20—C20—C21	120.6 (7)
O1—Zr—C6A	90.5 (3)	C19—C20—C21	119.1 (6)
O2—Zr—C6A	134.9 (3)	F21—C21—C22	120.6 (6)
O1—Zr—C7A	122.3 (3)	F21—C21—C20	119.4 (6)
O2—Zr—C7A	121.2 (3)	C22—C21—C20	120.0 (6)
O1—Zr—C8A	129.1 (3)	F22—C22—C21	117.9 (6)
O2—Zr—C8A	89.6 (3)	F22—C22—C17	119.3 (5)
O1—Zr—C9A	99.3 (4)	C21—C22—C17	122.7 (6)
O2—Zr—C9A	82.1 (3)	C24—C23—C27	100.6 (5)
O1—Zr—C10A	77.3 (2)	C24—C23—Si1	115.3 (4)
O2—Zr—C10A	107.4 (3)	C27—C23—Si1	117.5 (4)
O1—Zr—C6B	117.5 (5)	C24—C23—H23A	107.6
O2—Zr—C6B	77.4 (3)	C27—C23—H23A	107.6
O1—Zr—C7B	137.8 (3)	Si1—C23—H23A	107.6
O2—Zr—C7B	98.4 (5)	C25A—C24—C23	109.6 (6)
O1—Zr—C8B	113.8 (5)	C23—C24—C25B	102.8 (9)
O2—Zr—C8B	129.4 (4)	C25A—C24—H24A	109.7
O1—Zr—C9B	85.1 (4)	C23—C24—H24A	109.7
O2—Zr—C9B	124.4 (5)	C25B—C24—H24A	95.0
O1—Zr—C10B	87.5 (4)	C25A—C24—H24B	109.7
O2—Zr—C10B	92.1 (5)	C23—C24—H24B	109.7
C1—Zr—C4	51.9 (3)	C25B—C24—H24B	129.8
C1—Zr—C9A	156.4 (3)	H24A—C24—H24B	108.2
C1—Zr—C10A	128.9 (3)	C24—C25A—C26	104.5 (8)
C2—Zr—C1	31.7 (2)	C24—C25A—H25A	110.9
C2—Zr—C4	52.5 (2)	C26—C25A—H25A	110.9
C2—Zr—C9A	130.8 (3)	C24—C25A—H25B	110.9
C2—Zr—C10A	117.9 (3)	C26—C25A—H25B	110.9
C3—Zr—C1	52.5 (2)	H25A—C25A—H25B	108.9
C3—Zr—C2	32.2 (2)	C25B—C26—C27	107.8 (6)
C3—Zr—C4	31.6 (2)	C27—C26—C25A	103.1 (8)
C3—Zr—C6A	103.2 (4)	C25B—C26—H26A	90.7
C3—Zr—C7A	80.4 (3)	C27—C26—H26A	111.1
C3—Zr—C9A	124.3 (4)	C25A—C26—H26A	111.1
C3—Zr—C10A	132.8 (3)	C25B—C26—H26B	125.0
C3—Zr—C6B	107.4 (6)	C27—C26—H26B	111.1
C4—Zr—C9A	140.7 (4)	C25A—C26—H26B	111.1
C4—Zr—C10A	163.6 (3)	H26A—C26—H26B	109.1
C5—Zr—C1	31.9 (2)	C26—C27—C23	104.8 (6)
C5—Zr—C2	53.0 (3)	C26—C27—H27A	110.8
C5—Zr—C3	52.7 (3)	C23—C27—H27A	110.8
C5—Zr—C4	31.3 (3)	C26—C27—H27B	110.8
C5—Zr—C6A	135.4 (3)	C23—C27—H27B	110.8
C5—Zr—C7A	129.6 (3)	H27A—C27—H27B	108.9
C5—Zr—C9A	170.2 (4)	C26—C25B—C24	105.0 (8)
C5—Zr—C10A	158.1 (4)	C26—C25B—H25C	110.8
C5—Zr—C6B	153.6 (5)	C24—C25B—H25C	110.8
C5—Zr—C10B	174.1 (5)	C26—C25B—H25D	110.8
C6A—Zr—C1	103.7 (3)	C24—C25B—H25D	110.8
C6A—Zr—C2	86.2 (3)	H25C—C25B—H25D	108.8
C6A—Zr—C4	134.6 (3)	C32—C28—C29	102.3 (5)
C6A—Zr—C9A	52.8 (3)	C32—C28—Si2	114.9 (4)
C6A—Zr—C10A	32.1 (3)	C29—C28—Si2	115.2 (4)
C7A—Zr—C1	106.6 (3)	C32—C28—H28A	108.0
C7A—Zr—C2	77.8 (3)	C29—C28—H28A	108.0
C7A—Zr—C4	110.8 (3)	Si2—C28—H28A	108.0
C7A—Zr—C6A	31.8 (3)	C30—C29—C28	104.4 (5)
C7A—Zr—C9A	53.0 (3)	C30—C29—H29A	110.9
C7A—Zr—C10A	52.9 (3)	C28—C29—H29A	110.9
C8A—Zr—C1	135.2 (4)	C30—C29—H29B	110.9
C8A—Zr—C2	103.7 (4)	C28—C29—H29B	110.9
C8A—Zr—C3	92.4 (4)	H29A—C29—H29B	108.9
C8A—Zr—C4	113.6 (4)	C31—C30—C29	105.2 (6)
C8A—Zr—C5	143.9 (4)	C31—C30—H30A	110.7
C8A—Zr—C6A	52.8 (3)	C29—C30—H30A	110.7
C8A—Zr—C7A	32.1 (3)	C31—C30—H30B	110.7
C8A—Zr—C9A	32.0 (3)	C29—C30—H30B	110.7
C8A—Zr—C10A	52.6 (3)	H30A—C30—H30B	108.8
C9A—Zr—C10A	31.6 (3)	C32—C31—C30	108.2 (7)
C6B—Zr—C1	153.0 (5)	C32—C31—H31A	110.1
C6B—Zr—C2	121.5 (5)	C30—C31—H31A	110.1
C6B—Zr—C4	122.6 (5)	C32—C31—H31B	110.1
C7B—Zr—C1	120.9 (5)	C30—C31—H31B	110.1
C7B—Zr—C2	89.3 (5)	H31A—C31—H31B	108.4
C7B—Zr—C3	79.4 (4)	C31—C32—C28	106.0 (6)
C7B—Zr—C4	103.9 (4)	C31—C32—H32A	110.5
C7B—Zr—C5	132.0 (4)	C28—C32—H32A	110.5
C7B—Zr—C6B	32.2 (2)	C31—C32—H32B	110.5
C7B—Zr—C10B	53.4 (3)	C28—C32—H32B	110.5
C8B—Zr—C1	102.2 (4)	H32A—C32—H32B	108.7
C8B—Zr—C2	75.7 (4)	C34—C33—C37	104.1 (5)
C8B—Zr—C3	83.6 (5)	C34—C33—Si3	114.8 (4)
C8B—Zr—C4	115.0 (5)	C37—C33—Si3	114.8 (4)
C8B—Zr—C5	128.7 (4)	C34—C33—H33A	107.6
C8B—Zr—C6B	53.6 (3)	C37—C33—H33A	107.6
C8B—Zr—C7B	32.5 (2)	Si3—C33—H33A	107.6
C8B—Zr—C9B	32.6 (2)	C35—C34—C33	103.5 (6)
C8B—Zr—C10B	53.7 (3)	C35—C34—H34A	111.1
C9B—Zr—C1	114.2 (5)	C33—C34—H34A	111.1
C9B—Zr—C2	98.8 (6)	C35—C34—H34B	111.1
C9B—Zr—C3	115.1 (6)	C33—C34—H34B	111.1
C9B—Zr—C4	146.7 (6)	H34A—C34—H34B	109.0
C9B—Zr—C5	146.1 (5)	C36—C35—C34	106.4 (6)
C9B—Zr—C6B	53.5 (3)	C36—C35—H35A	110.5
C9B—Zr—C7B	53.8 (3)	C34—C35—H35A	110.5
C9B—Zr—C10B	32.3 (2)	C36—C35—H35B	110.5
C10B—Zr—C1	145.9 (6)	C34—C35—H35B	110.5
C10B—Zr—C2	128.7 (4)	H35A—C35—H35B	108.6
C10B—Zr—C3	132.3 (4)	C35—C36—C37	108.0 (6)
C10B—Zr—C4	154.6 (5)	C35—C36—H36A	110.1
C10B—Zr—C10A	17.5 (4)	C37—C36—H36A	110.1
C10B—Zr—C6B	32.1 (2)	C35—C36—H36B	110.1
O1—Si1—O7	109.3 (2)	C37—C36—H36B	110.1
O1—Si1—O8	110.2 (2)	H36A—C36—H36B	108.4
O7—Si1—O8	108.79 (19)	C36—C37—C33	106.6 (5)
O1—Si1—C23	111.5 (2)	C36—C37—H37A	110.4
O7—Si1—C23	109.8 (2)	C33—C37—H37A	110.4
O8—Si1—C23	107.2 (3)	C36—C37—H37B	110.4
O2—Si2—O9	110.7 (2)	C33—C37—H37B	110.4
O2—Si2—O4	108.3 (2)	H37A—C37—H37B	108.6
O9—Si2—O4	108.7 (2)	C39—C38—C42	102.7 (5)
O2—Si2—C28	111.0 (2)	C39—C38—Si4	112.7 (4)
O9—Si2—C28	108.1 (2)	C42—C38—Si4	115.4 (4)
O4—Si2—C28	110.0 (2)	C39—C38—H38A	108.6
O6—Si3—O5	109.4 (2)	C42—C38—H38A	108.6
O6—Si3—O3	108.5 (2)	Si4—C38—H38A	108.6
O5—Si3—O3	105.8 (2)	C40—C39—C38	108.6 (5)
O6—Si3—C33	112.5 (2)	C40—C39—H39A	110.0
O5—Si3—C33	111.9 (2)	C38—C39—H39A	110.0
O3—Si3—C33	108.5 (2)	C40—C39—H39B	110.0
O8—Si4—O9	110.4 (2)	C38—C39—H39B	110.0
O8—Si4—O10	108.6 (2)	H39A—C39—H39B	108.4
O9—Si4—O10	108.9 (2)	C39—C40—C41	105.5 (6)
O8—Si4—C38	110.4 (2)	C39—C40—H40A	110.6
O9—Si4—C38	110.9 (2)	C41—C40—H40A	110.6
O10—Si4—C38	107.4 (2)	C39—C40—H40B	110.6
O7—Si5—O11	110.1 (2)	C41—C40—H40B	110.6
O7—Si5—O6	108.2 (2)	H40A—C40—H40B	108.8
O11—Si5—O6	108.9 (2)	C42—C41—C40	105.7 (6)
O7—Si5—C43	112.2 (2)	C42—C41—H41A	110.6
O11—Si5—C43	109.7 (2)	C40—C41—H41A	110.6
O6—Si5—C43	107.6 (2)	C42—C41—H41B	110.6
O4—Si6—O12	110.3 (2)	C40—C41—H41B	110.6
O4—Si6—O5	107.66 (19)	H41A—C41—H41B	108.7
O12—Si6—O5	109.2 (2)	C41—C42—C38	105.2 (5)
O4—Si6—C48	109.3 (2)	C41—C42—H42A	110.7
O12—Si6—C48	110.4 (2)	C38—C42—H42A	110.7
O5—Si6—C48	109.8 (2)	C41—C42—H42B	110.7
O10—Si7—O12	109.8 (2)	C38—C42—H42B	110.7
O10—Si7—O11	109.5 (2)	H42A—C42—H42B	108.8
O12—Si7—O11	108.1 (2)	C44—C43—C47	104.8 (4)
O10—Si7—C53	107.5 (2)	C44—C43—Si5	114.2 (4)
O12—Si7—C53	110.0 (2)	C47—C43—Si5	113.7 (4)
O11—Si7—C53	112.0 (2)	C44—C43—H43A	107.9
Si1—O1—Zr	154.4 (2)	C47—C43—H43A	107.9
Si2—O2—Zr	153.7 (2)	Si5—C43—H43A	107.9
B—O3—Si3	168.4 (4)	C45—C44—C43	105.1 (5)
Si6—O4—Si2	156.4 (3)	C45—C44—H44A	110.7
Si3—O5—Si6	148.9 (3)	C43—C44—H44A	110.7
Si3—O6—Si5	147.4 (2)	C45—C44—H44B	110.7
Si5—O7—Si1	163.0 (3)	C43—C44—H44B	110.7
Si4—O8—Si1	150.9 (3)	H44A—C44—H44B	108.8
Si4—O9—Si2	145.5 (3)	C46—C45—C44	103.6 (5)
Si7—O10—Si4	148.6 (3)	C46—C45—H45A	111.0
Si7—O11—Si5	145.2 (3)	C44—C45—H45A	111.0
Si6—O12—Si7	148.2 (2)	C46—C45—H45B	111.0
C2—C1—C5	108.9 (7)	C44—C45—H45B	111.0
C2—C1—Zr	74.1 (4)	H45A—C45—H45B	109.0
C5—C1—Zr	73.5 (4)	C45—C46—C47	103.8 (5)
C2—C1—H1A	125.3	C45—C46—H46A	111.0
C5—C1—H1A	125.3	C47—C46—H46A	111.0
Zr—C1—H1A	125.3	C45—C46—H46B	111.0
C1—C2—C3	106.9 (7)	C47—C46—H46B	111.0
C1—C2—Zr	74.2 (4)	H46A—C46—H46B	109.0
C3—C2—Zr	73.7 (4)	C46—C47—C43	105.8 (5)
C1—C2—H2A	126.1	C46—C47—H47A	110.6
C3—C2—H2A	126.1	C43—C47—H47A	110.6
Zr—C2—H2A	126.1	C46—C47—H47B	110.6
C4—C3—C2	107.5 (8)	C43—C47—H47B	110.6
C4—C3—Zr	74.7 (4)	H47A—C47—H47B	108.7
C2—C3—Zr	74.1 (4)	C52—C48—C49	103.7 (5)
C4—C3—H3A	125.8	C52—C48—Si6	114.8 (4)
C2—C3—H3A	125.8	C49—C48—Si6	114.0 (4)
Zr—C3—H3A	125.8	C52—C48—H48A	108.0
C5—C4—C3	109.3 (8)	C49—C48—H48A	108.0
C5—C4—Zr	73.5 (4)	Si6—C48—H48A	108.0
C3—C4—Zr	73.6 (4)	C50—C49—C48	105.5 (5)
C5—C4—H4A	125.1	C50—C49—H49A	110.6
C3—C4—H4A	125.1	C48—C49—H49A	110.6
Zr—C4—H4A	125.1	C50—C49—H49B	110.6
C4—C5—C1	107.4 (8)	C48—C49—H49B	110.6
C4—C5—Zr	75.2 (5)	H49A—C49—H49B	108.8
C1—C5—Zr	74.6 (4)	C51B—C50—C49	108.3 (7)
C4—C5—H5A	125.7	C51A—C50—C49	110.6 (7)
C1—C5—H5A	125.7	C51B—C50—H50A	134.5
Zr—C5—H5A	125.7	C51A—C50—H50A	109.5
C7A—C6A—C10A	108.3 (8)	C49—C50—H50A	109.5
C7A—C6A—Zr	74.1 (6)	C51B—C50—H50B	81.7
C10A—C6A—Zr	74.8 (5)	C51A—C50—H50B	109.5
C7A—C6A—H6A	125.4	C49—C50—H50B	109.5
C10A—C6A—H6A	125.4	H50A—C50—H50B	108.1
Zr—C6A—H6A	125.4	C50—C51A—C52	103.8 (8)
C6A—C7A—C8A	107.5 (9)	C50—C51A—H51A	111.0
C6A—C7A—Zr	74.1 (6)	C52—C51A—H51A	111.0
C8A—C7A—Zr	73.4 (6)	C50—C51A—H51B	111.0
C6A—C7A—H7A	125.9	C52—C51A—H51B	111.0
C8A—C7A—H7A	125.9	H51A—C51A—H51B	109.0
Zr—C7A—H7A	125.9	C51A—C52—C48	110.6 (6)
C7A—C8A—C9A	108.7 (9)	C48—C52—C51B	99.0 (7)
C7A—C8A—Zr	74.5 (6)	C51A—C52—H52A	109.5
C9A—C8A—Zr	75.4 (6)	C48—C52—H52A	109.5
C7A—C8A—H8A	125.2	C51B—C52—H52A	89.7
C9A—C8A—H8A	125.2	C51A—C52—H52B	109.5
Zr—C8A—H8A	125.2	C48—C52—H52B	109.5
C10A—C9A—C8A	107.5 (8)	C51B—C52—H52B	138.1
C10A—C9A—Zr	74.2 (6)	H52A—C52—H52B	108.1
C8A—C9A—Zr	72.6 (6)	C50—C51B—C52	104.2 (7)
C10A—C9A—H9A	125.9	C50—C51B—H51C	110.9
C8A—C9A—H9A	125.9	C52—C51B—H51C	110.9
Zr—C9A—H9A	125.9	C50—C51B—H51D	110.9
C9A—C10A—C6A	108.0 (8)	C52—C51B—H51D	110.9
C9A—C10A—Zr	74.2 (6)	H51C—C51B—H51D	108.9
C6A—C10A—Zr	73.1 (5)	C57—C53—C54	105.9 (5)
C9A—C10A—H10A	125.7	C57—C53—Si7	117.3 (4)
C6A—C10A—H10A	125.7	C54—C53—Si7	111.3 (4)
Zr—C10A—H10A	125.7	C57—C53—H53A	107.3
C10B—C6B—C7B	108.0	C54—C53—H53A	107.3
C10B—C6B—Zr	73.6 (6)	Si7—C53—H53A	107.3
C7B—C6B—Zr	73.0 (7)	C55A—C54—C53	105.5 (7)
C10B—C6B—H6B	125.7	C53—C54—C55B	102.0 (11)
C7B—C6B—H6B	125.7	C55A—C54—H54A	110.6
Zr—C6B—H6B	125.7	C53—C54—H54A	110.6
C8B—C7B—C6B	108.0	C55B—C54—H54A	85.7
C8B—C7B—Zr	72.8 (6)	C55A—C54—H54B	110.6
C6B—C7B—Zr	74.9 (6)	C53—C54—H54B	110.6
C8B—C7B—H7B	125.7	C55B—C54—H54B	135.6
C6B—C7B—H7B	125.7	H54A—C54—H54B	108.8
Zr—C7B—H7B	125.7	C54—C55A—C56A	101.7 (8)
C7B—C8B—C9B	108.0	C54—C55A—H55A	111.4
C7B—C8B—Zr	74.7 (6)	C56A—C55A—H55A	111.4
C9B—C8B—Zr	74.0 (6)	C54—C55A—H55B	111.4
C7B—C8B—H8B	125.6	C56A—C55A—H55B	111.4
C9B—C8B—H8B	125.6	H55A—C55A—H55B	109.3
Zr—C8B—H8B	125.6	C57—C56A—C55A	101.1 (9)
C8B—C9B—C10B	108.0	C57—C56A—H56A	111.5
C8B—C9B—Zr	73.3 (6)	C55A—C56A—H56A	111.5
C10B—C9B—Zr	75.0 (6)	C57—C56A—H56B	111.5
C8B—C9B—H9B	125.6	C55A—C56A—H56B	111.5
C10B—C9B—H9B	125.6	H56A—C56A—H56B	109.4
Zr—C9B—H9B	125.6	C56A—C57—C53	102.9 (7)
C6B—C10B—C9B	108.0	C56B—C57—C53	103.0 (11)
C6B—C10B—Zr	74.3 (6)	C56A—C57—H57A	111.2
C9B—C10B—Zr	72.6 (7)	C56B—C57—H57A	80.7
C6B—C10B—H10B	125.7	C53—C57—H57A	111.2
C9B—C10B—H10B	125.7	C56A—C57—H57B	111.2
Zr—C10B—H10B	125.7	C56B—C57—H57B	136.9
C12—C11—C16	113.1 (5)	C53—C57—H57B	111.2
C12—C11—B	123.2 (5)	H57A—C57—H57B	109.1
C16—C11—B	123.7 (5)	C56B—C55B—C54	98.0 (15)
F12—C12—C13	116.6 (5)	C56B—C55B—H55C	112.2
F12—C12—C11	119.6 (5)	C54—C55B—H55C	112.2
C13—C12—C11	123.7 (5)	C56B—C55B—H55D	112.2
F13—C13—C12	120.7 (6)	C54—C55B—H55D	112.2
F13—C13—C14	119.2 (6)	H55C—C55B—H55D	109.8
C12—C13—C14	120.1 (6)	C57—C56B—C55B	100.0 (15)
F14—C14—C13	121.2 (6)	C57—C56B—H56C	111.8
F14—C14—C15	119.5 (6)	C55B—C56B—H56C	111.8
C13—C14—C15	119.3 (6)	C57—C56B—H56D	111.8
F15—C15—C16	121.2 (6)	C55B—C56B—H56D	111.8
F15—C15—C14	119.6 (6)	H56C—C56B—H56D	109.5
C16—C15—C14	119.2 (6)	O3—B—C11	119.3 (5)
F16—C16—C15	116.3 (5)	O3—B—C17	119.1 (6)
F16—C16—C11	119.1 (5)	C11—B—C17	121.6 (5)
C15—C16—C11	124.6 (6)