Dichlorido(η⁵-cyclo­penta­dien­yl)[N-(2,6-dimethyl­phen­yl)-N′-({(2,6-dimethyl­phen­yl)[imino­(phen­yl)methyl-κN]amino}dimethyl­silyl)benzamidinato-κ²N,N′]zirconium(IV) dichloro­methane solvate

The Zr^IV atom in the title half-sandwich organometallic zirconium(IV) compound, [Zr(C₅H₅)(C₃₂H₃₅N₄Si)Cl₂]·CH₂Cl₂, is N,N′,N′′-chelated by the silyl-linked imino-amidinato monoanion in the first example of such an organozirconium derivative. The three N-donor atoms along with a Cl atom form a square, above and below which are the cyclo­penta­dieny ring and the second Cl atom. The coordination geometry is octa­hedral.

Key indicators

• Single-crystal X-ray study
• T = 213 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.042
• wR factor = 0.102
• Data-to-parameter ratio = 15.2

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.605     0.835
            Tmin(prime) and Tmax expected:      0.728     0.829
            RR(prime) =      0.825
            Please check that your absorption correction is appropriate.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.98
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large .............       0.82
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        200 Deg.
PLAT220_ALERT_2_C Large Non-Solvent    C     Ueq(max)/Ueq(min) ...       3.10 Ratio
PLAT222_ALERT_3_C Large Non-Solvent    H     Ueq(max)/Ueq(min) ...       3.06 Ratio
PLAT244_ALERT_4_C Low   'Solvent' Ueq as Compared to Neighbors for        C38

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   7 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   4 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

The growing interest of the organometallic compounds incorporated with the dianionic linked bis(amidinate) ligands (Hill et al., 2006; Li et al., 2003) and widely applications of the half-sandwich compounds (Terasawa et al., 2005) attracted us to the subject.

The title compound is the first half-sandwich compound with the silyl-linked-imino-amidinato ligand. It was obtained from the reaction of ZrCl₃(C₅H₅) with [SiMe₂{NC(Ph)N(2,6-Me₂Ph)Li}₂]. The N-donor ligand coordinates to Zr center in tridentate mode, which is not the same as that in the lithium substrate. It results from an interesting rearrangement process (Bai et al., 2006). In the molecular structure of the title compound, the amidinate moiety binds the metal center with N—Zr—N angle of 59.66 (9)°, slightly smaller than the corresponding value in the related {Zr(C₅H₅)[C(Ph)(NSiMe₃)₂]Cl₂}(Gómez et al.,1995). On one end of the amidinate unit, the pendant imino group coordinates the metal center and contributes the six-membered ring configuration, Zr1—N2—Si1—N3—C26—N4. The three Zr—N bonds are slightly longer than 2.2 Å in the normal range and they are coplanar. The angle between the [ZrN₃] plane and the pentagon plane of the cyclopentadienyl is 88.9°, indicating the perpendicular relationship between them. Such situation is very special and rare because the cyclopentadienyl is usually on the side of amidinate ligand in most cases. In the title compound, the distance of Zr—Cp_centroid is 2.225 Å, also in the [ZrN₃] plane. Two Cl atoms are separated by the N-donor ligand. Thus, it displays the distorted octahedral geometry around the Zr ion.

Related literature

The compound is a half-sandwich compound. For related compounds and their applications, see: Gómez et al. (1995); Terasawa et al. (2005). For other organometallic compounds with similar bis(amidinate) ligands, see: Hill et al. (2006); Li et al. (2003). For the mechanism of the N-donor ligand rearrangement, see: Bai et al. (2006).

S2. Experimental

ZrCl₃(C₅H₅) (0.46 g, 1.75 mmol) was added into the solution of [SiMe₂{NC(Ph)N(2,6-Me₂Ph)Li}₂] (1.75 mmol) in THF (20 ml) at 273 K. The reaction mixture was warmed to room temperature and kept stirring for 12 h. It was dried in vacuum to remove all volatiles and the residue was extracted with CH₂Cl₂ (25 ml). Concentration of the filtrate under reduced pressure gave the title compound as colorless crystals (yield 0.86 g, 60%). CHN analysis, calculated for C₃₇H₄₀Cl₂N₄SiZr (730.96): C 60.80, H 5.52, N 7.66%; found: C 60.33, H 5.17, N 7.37%. Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃, δ, p.p.m.): 7.37–6.93 (m, 16H; phenyls), 6.50 (s, 5H; Cp), 2.56–2.45 (m, 12H; methyls), 0.50 (s, 6H; SiMe₂); ¹³C NMR (75 MHz, CDCl₃, δ, p.p.m.): 180.5, 177.1 (N—C—N), 147.8–120.5 (phenyls), 23.3, 22.6 (methyls), 7.7, 5.2 (SiMe₂).

S3. Refinement

All H atoms were initially located in a difference Fourier map. The methyl H atoms were then constrained to an ideal geometry, with C—H distances of 0.96Å and U_iso(H) = 1.2U_eq(C), but each group was allowed to rotate freely about its C–C bond. The other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances in the range 0.93Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL/PC (Sheldrick, 1999); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. Molecular structure of the title compound, showing the atom-lebelling scheme and 30% probability displacement ellipsoids. H atoms are not shown.

Dichlorido(η⁵-cyclopentadienyl)[N-(2,6-dimethylphenyl)-N'- ({(2,6-dimethylphenyl)[imino(phenyl)methyl- κN]amino}dimethylsilyl)benzamidinato-κ²N,N']zirconium(IV) dichloromethane monosolvate

Crystal data

[Zr(C5H5)(C32H35N4Si)Cl2]·CH2Cl2	Z = 2
Mr = 815.87	F(000) = 840
Triclinic, P1	Dx = 1.401 Mg m^−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.5134 (13) Å	Cell parameters from 6394 reflections
b = 15.206 (2) Å	θ = 2.2–27.7°
c = 15.369 (2) Å	µ = 0.62 mm^−1
α = 115.042 (2)°	T = 213 K
β = 103.692 (2)°	Prism, colorless
γ = 92.069 (2)°	0.50 × 0.30 × 0.30 mm
V = 1933.5 (4) Å^3

Data collection

Bruker Smart CCD-detector diffractometer	6657 independent reflections
Radiation source: fine-focus sealed tube	6186 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.017
ϕ and ω scan	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→11
Tmin = 0.605, Tmax = 0.835	k = −18→11
7987 measured reflections	l = −18→18

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H-atom parameters constrained
S = 1.09	w = 1/[σ^2(Fo^2) + (0.0435P)^2 + 1.5172P] where P = (Fo^2 + 2Fc^2)/3
6657 reflections	(Δ/σ)max = 0.001
437 parameters	Δρmax = 0.71 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

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 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
Zr1	−0.10953 (3)	0.17095 (2)	0.14783 (2)	0.02311 (10)
Si1	0.25585 (8)	0.26176 (6)	0.31212 (6)	0.02434 (18)
Cl1	0.04791 (8)	0.16067 (6)	0.03096 (6)	0.03238 (18)
Cl2	−0.16730 (9)	0.19957 (6)	0.30950 (6)	0.0372 (2)
N1	−0.1045 (3)	0.32972 (18)	0.18845 (19)	0.0303 (6)
N2	0.0881 (3)	0.27996 (17)	0.25785 (18)	0.0250 (5)
N3	0.2134 (3)	0.15896 (17)	0.33685 (18)	0.0253 (5)
N4	0.0322 (3)	0.06850 (18)	0.18635 (18)	0.0273 (5)
H4A	0.0274	0.0126	0.1352	0.033*
C1	−0.1864 (3)	0.4020 (2)	0.1722 (3)	0.0365 (8)
C2	−0.2740 (4)	0.4472 (2)	0.2348 (3)	0.0446 (9)
C3	−0.3541 (5)	0.5162 (3)	0.2178 (4)	0.0646 (12)
H3A	−0.4124	0.5479	0.2599	0.078*
C4	−0.3494 (5)	0.5385 (3)	0.1411 (4)	0.0762 (15)
H4B	−0.4033	0.5857	0.1311	0.091*
C5	−0.2660 (5)	0.4922 (3)	0.0791 (4)	0.0683 (13)
H5A	−0.2650	0.5069	0.0257	0.082*
C6	−0.1822 (4)	0.4234 (3)	0.0931 (3)	0.0489 (9)
C7	−0.2843 (4)	0.4238 (3)	0.3191 (3)	0.0571 (11)
H7A	−0.3657	0.4509	0.3436	0.086*
H7B	−0.1941	0.4523	0.3728	0.086*
H7C	−0.2998	0.3531	0.2952	0.086*
C8	−0.0910 (5)	0.3759 (3)	0.0237 (3)	0.0675 (12)
H8A	0.0120	0.3976	0.0601	0.101*
H8B	−0.1128	0.3944	−0.0306	0.101*
H8C	−0.1129	0.3051	−0.0032	0.101*
C9	0.0321 (3)	0.3547 (2)	0.2486 (2)	0.0253 (6)
C10	0.1137 (3)	0.4568 (2)	0.2996 (2)	0.0283 (7)
C11	0.1057 (4)	0.5217 (3)	0.3922 (3)	0.0462 (9)
H11A	0.0457	0.5024	0.4236	0.055*
C12	0.1856 (5)	0.6157 (3)	0.4402 (3)	0.0629 (12)
H12A	0.1794	0.6597	0.5039	0.075*
C13	0.2720 (5)	0.6442 (3)	0.3958 (4)	0.0630 (13)
H13A	0.3254	0.7081	0.4284	0.076*
C14	0.2820 (5)	0.5804 (4)	0.3036 (4)	0.0735 (14)
H14A	0.3422	0.6005	0.2729	0.088*
C15	0.2036 (5)	0.4858 (3)	0.2550 (3)	0.0575 (11)
H15A	0.2119	0.4418	0.1920	0.069*
C16	0.3602 (4)	0.3661 (2)	0.4316 (2)	0.0357 (7)
H16A	0.3002	0.3852	0.4778	0.054*
H16B	0.3865	0.4212	0.4194	0.054*
H16C	0.4483	0.3465	0.4603	0.054*
C17	0.3718 (3)	0.2264 (2)	0.2254 (2)	0.0337 (7)
H17A	0.3181	0.1718	0.1625	0.051*
H17B	0.4599	0.2071	0.2545	0.051*
H17C	0.3982	0.2819	0.2137	0.051*
C18	0.3032 (3)	0.1606 (2)	0.4293 (2)	0.0305 (7)
C19	0.4297 (3)	0.1167 (2)	0.4282 (3)	0.0357 (8)
C20	0.5108 (4)	0.1183 (3)	0.5179 (3)	0.0467 (10)
H20A	0.5952	0.0880	0.5190	0.056*
C21	0.4692 (4)	0.1633 (3)	0.6040 (3)	0.0510 (10)
H21A	0.5247	0.1627	0.6631	0.061*
C22	0.3473 (4)	0.2091 (3)	0.6050 (3)	0.0472 (9)
H22A	0.3213	0.2408	0.6650	0.057*
C23	0.2618 (4)	0.2089 (2)	0.5173 (2)	0.0359 (8)
C24	0.4833 (4)	0.0687 (3)	0.3373 (3)	0.0485 (9)
H24A	0.4066	0.0591	0.2784	0.073*
H24B	0.5095	0.0056	0.3309	0.073*
H24C	0.5686	0.1104	0.3437	0.073*
C25	0.1288 (4)	0.2592 (3)	0.5212 (3)	0.0443 (9)
H25A	0.0443	0.2125	0.5069	0.066*
H25B	0.1118	0.2845	0.4719	0.066*
H25C	0.1444	0.3131	0.5873	0.066*
C26	0.1199 (3)	0.0764 (2)	0.2700 (2)	0.0246 (6)
C27	0.1091 (3)	−0.0107 (2)	0.2926 (2)	0.0285 (7)
C28	0.1635 (4)	−0.0944 (2)	0.2420 (3)	0.0406 (8)
H28A	0.2149	−0.0961	0.1962	0.049*
C29	0.1429 (4)	−0.1763 (3)	0.2584 (3)	0.0489 (9)
H29A	0.1816	−0.2329	0.2244	0.059*
C30	0.0667 (5)	−0.1750 (3)	0.3236 (3)	0.0515 (10)
H30A	0.0533	−0.2304	0.3350	0.062*
C31	0.0099 (5)	−0.0925 (3)	0.3722 (3)	0.0644 (12)
H31A	−0.0440	−0.0919	0.4164	0.077*
C32	0.0308 (5)	−0.0100 (3)	0.3573 (3)	0.0529 (10)
H32A	−0.0084	0.0464	0.3914	0.063*
C33	−0.2591 (3)	0.0458 (3)	−0.0229 (2)	0.0394 (8)
H33A	−0.2200	0.0066	−0.0795	0.047*
C34	−0.3107 (4)	0.1349 (3)	−0.0057 (3)	0.0410 (8)
H34A	−0.3160	0.1688	−0.0488	0.049*
C35	−0.3781 (3)	0.1577 (2)	0.0716 (2)	0.0375 (8)
H35A	−0.4375	0.2111	0.0927	0.045*
C36	−0.3691 (3)	0.0831 (2)	0.1009 (2)	0.0367 (8)
H36A	−0.4184	0.0754	0.1477	0.044*
C37	−0.2939 (3)	0.0147 (2)	0.0438 (2)	0.0359 (8)
H37A	−0.2816	−0.0499	0.0432	0.043*
C38	0.2517 (5)	0.2429 (4)	0.9050 (4)	0.0799 (15)
H38A	0.1779	0.2089	0.9198	0.096*
H38B	0.2009	0.2773	0.8686	0.096*
Cl3	0.37352 (15)	0.32951 (10)	1.01815 (10)	0.0853 (4)
Cl4	0.3398 (2)	0.15686 (15)	0.82979 (12)	0.1207 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.02140 (16)	0.02120 (16)	0.02449 (16)	0.00268 (11)	0.00554 (11)	0.00857 (12)
Si1	0.0224 (4)	0.0229 (4)	0.0267 (4)	0.0012 (3)	0.0054 (3)	0.0111 (3)
Cl1	0.0329 (4)	0.0351 (4)	0.0304 (4)	0.0038 (3)	0.0122 (3)	0.0141 (3)
Cl2	0.0362 (4)	0.0421 (5)	0.0303 (4)	0.0029 (4)	0.0140 (3)	0.0112 (4)
N1	0.0273 (13)	0.0236 (13)	0.0353 (15)	0.0047 (11)	0.0033 (11)	0.0113 (11)
N2	0.0245 (12)	0.0225 (13)	0.0268 (13)	0.0030 (10)	0.0060 (10)	0.0105 (11)
N3	0.0258 (13)	0.0259 (13)	0.0256 (13)	0.0036 (11)	0.0051 (10)	0.0136 (11)
N4	0.0295 (13)	0.0233 (13)	0.0240 (13)	0.0064 (11)	0.0058 (11)	0.0064 (11)
C1	0.0304 (17)	0.0236 (16)	0.046 (2)	0.0035 (14)	−0.0015 (15)	0.0134 (15)
C2	0.0344 (19)	0.0292 (18)	0.055 (2)	0.0071 (15)	0.0028 (17)	0.0094 (17)
C3	0.048 (2)	0.042 (2)	0.088 (3)	0.0205 (19)	0.010 (2)	0.017 (2)
C4	0.063 (3)	0.051 (3)	0.110 (4)	0.024 (2)	0.003 (3)	0.041 (3)
C5	0.076 (3)	0.049 (3)	0.083 (3)	0.018 (2)	0.003 (3)	0.042 (3)
C6	0.052 (2)	0.037 (2)	0.058 (2)	0.0065 (17)	0.0030 (19)	0.0266 (19)
C7	0.047 (2)	0.048 (2)	0.068 (3)	0.0167 (19)	0.024 (2)	0.013 (2)
C8	0.093 (3)	0.062 (3)	0.067 (3)	0.021 (3)	0.026 (3)	0.044 (2)
C9	0.0291 (16)	0.0240 (15)	0.0245 (15)	0.0038 (13)	0.0104 (13)	0.0108 (13)
C10	0.0249 (15)	0.0261 (16)	0.0336 (17)	0.0040 (13)	0.0040 (13)	0.0153 (14)
C11	0.049 (2)	0.037 (2)	0.040 (2)	−0.0009 (17)	0.0145 (17)	0.0055 (16)
C12	0.056 (3)	0.035 (2)	0.060 (3)	0.003 (2)	0.004 (2)	−0.0066 (19)
C13	0.046 (2)	0.029 (2)	0.094 (4)	−0.0032 (18)	−0.006 (2)	0.023 (2)
C14	0.063 (3)	0.062 (3)	0.108 (4)	−0.011 (2)	0.026 (3)	0.050 (3)
C15	0.065 (3)	0.050 (2)	0.059 (3)	−0.006 (2)	0.029 (2)	0.020 (2)
C16	0.0368 (18)	0.0310 (17)	0.0324 (18)	−0.0023 (14)	0.0014 (14)	0.0126 (14)
C17	0.0301 (16)	0.0360 (18)	0.0394 (19)	0.0074 (14)	0.0139 (14)	0.0185 (15)
C18	0.0321 (16)	0.0277 (16)	0.0334 (17)	−0.0024 (13)	0.0013 (14)	0.0198 (14)
C19	0.0295 (17)	0.0282 (17)	0.047 (2)	−0.0034 (14)	−0.0003 (15)	0.0210 (16)
C20	0.0348 (19)	0.037 (2)	0.065 (3)	−0.0026 (16)	−0.0084 (18)	0.0314 (19)
C21	0.060 (2)	0.044 (2)	0.041 (2)	−0.0063 (19)	−0.0112 (19)	0.0256 (19)
C22	0.060 (2)	0.046 (2)	0.036 (2)	−0.0011 (19)	0.0030 (17)	0.0240 (17)
C23	0.0445 (19)	0.0331 (18)	0.0299 (17)	−0.0018 (15)	0.0061 (15)	0.0168 (15)
C24	0.038 (2)	0.046 (2)	0.066 (3)	0.0140 (17)	0.0141 (18)	0.029 (2)
C25	0.056 (2)	0.047 (2)	0.0344 (19)	0.0099 (18)	0.0192 (17)	0.0183 (17)
C26	0.0256 (15)	0.0238 (15)	0.0256 (15)	0.0055 (12)	0.0115 (12)	0.0096 (13)
C27	0.0277 (15)	0.0274 (16)	0.0278 (16)	−0.0013 (13)	0.0018 (13)	0.0135 (13)
C28	0.051 (2)	0.0344 (19)	0.047 (2)	0.0122 (16)	0.0224 (17)	0.0225 (17)
C29	0.062 (2)	0.0311 (19)	0.059 (2)	0.0126 (18)	0.019 (2)	0.0237 (18)
C30	0.071 (3)	0.037 (2)	0.053 (2)	−0.0006 (19)	0.010 (2)	0.0309 (19)
C31	0.095 (3)	0.051 (3)	0.072 (3)	0.010 (2)	0.048 (3)	0.037 (2)
C32	0.075 (3)	0.037 (2)	0.063 (3)	0.0140 (19)	0.042 (2)	0.0252 (19)
C33	0.0268 (17)	0.042 (2)	0.0306 (18)	−0.0044 (15)	0.0067 (14)	−0.0004 (15)
C34	0.0341 (18)	0.047 (2)	0.0369 (19)	−0.0032 (16)	−0.0034 (15)	0.0218 (17)
C35	0.0233 (16)	0.0363 (19)	0.0408 (19)	0.0061 (14)	0.0025 (14)	0.0092 (15)
C36	0.0231 (16)	0.043 (2)	0.0351 (18)	−0.0068 (14)	0.0048 (14)	0.0123 (16)
C37	0.0250 (16)	0.0281 (17)	0.0423 (19)	−0.0022 (13)	−0.0010 (14)	0.0101 (15)
C38	0.065 (3)	0.101 (4)	0.084 (4)	−0.011 (3)	0.013 (3)	0.057 (3)
Cl3	0.0939 (9)	0.0799 (9)	0.0864 (9)	0.0132 (7)	0.0027 (7)	0.0525 (8)
Cl4	0.1454 (15)	0.1500 (16)	0.0749 (10)	0.0516 (13)	0.0290 (10)	0.0562 (11)

Geometric parameters (Å, º)

Zr1—N1	2.219 (2)	C15—H15A	0.9400
Zr1—N2	2.245 (2)	C16—H16A	0.9700
Zr1—N4	2.270 (2)	C16—H16B	0.9700
Zr1—C34	2.495 (3)	C16—H16C	0.9700
Zr1—C35	2.508 (3)	C17—H17A	0.9700
Zr1—C33	2.518 (3)	C17—H17B	0.9700
Zr1—Cl2	2.5326 (9)	C17—H17C	0.9700
Zr1—C37	2.536 (3)	C18—C19	1.397 (4)
Zr1—C36	2.550 (3)	C18—C23	1.397 (5)
Zr1—Cl1	2.5588 (8)	C19—C20	1.401 (5)
Zr1—C9	2.664 (3)	C19—C24	1.499 (5)
Si1—N2	1.708 (2)	C20—C21	1.370 (6)
Si1—N3	1.811 (2)	C20—H20A	0.9400
Si1—C17	1.847 (3)	C21—C22	1.374 (5)
Si1—C16	1.853 (3)	C21—H21A	0.9400
N1—C9	1.336 (4)	C22—C23	1.399 (5)
N1—C1	1.442 (4)	C22—H22A	0.9400
N2—C9	1.319 (4)	C23—C25	1.502 (5)
N3—C26	1.348 (4)	C24—H24A	0.9700
N3—C18	1.465 (4)	C24—H24B	0.9700
N4—C26	1.310 (4)	C24—H24C	0.9700
N4—H4A	0.8700	C25—H25A	0.9700
C1—C6	1.394 (5)	C25—H25B	0.9700
C1—C2	1.399 (5)	C25—H25C	0.9700
C2—C3	1.394 (5)	C26—C27	1.510 (4)
C2—C7	1.504 (6)	C27—C32	1.374 (5)
C3—C4	1.368 (7)	C27—C28	1.376 (4)
C3—H3A	0.9400	C28—C29	1.387 (5)
C4—C5	1.366 (7)	C28—H28A	0.9400
C4—H4B	0.9400	C29—C30	1.363 (5)
C5—C6	1.394 (5)	C29—H29A	0.9400
C5—H5A	0.9400	C30—C31	1.368 (6)
C6—C8	1.498 (6)	C30—H30A	0.9400
C7—H7A	0.9700	C31—C32	1.384 (5)
C7—H7B	0.9700	C31—H31A	0.9400
C7—H7C	0.9700	C32—H32A	0.9400
C8—H8A	0.9700	C33—C37	1.394 (5)
C8—H8B	0.9700	C33—C34	1.398 (5)
C8—H8C	0.9700	C33—H33A	0.9900
C9—C10	1.491 (4)	C34—C35	1.405 (5)
C10—C11	1.368 (5)	C34—H34A	0.9900
C10—C15	1.380 (5)	C35—C36	1.384 (5)
C11—C12	1.389 (5)	C35—H35A	0.9900
C11—H11A	0.9400	C36—C37	1.393 (5)
C12—C13	1.348 (6)	C36—H36A	0.9900
C12—H12A	0.9400	C37—H37A	0.9900
C13—C14	1.366 (7)	C38—Cl4	1.735 (6)
C13—H13A	0.9400	C38—Cl3	1.760 (5)
C14—C15	1.390 (6)	C38—H38A	0.9800
C14—H14A	0.9400	C38—H38B	0.9800
N1—Zr1—N2	59.62 (9)	C10—C11—H11A	119.7
N1—Zr1—N4	139.71 (9)	C12—C11—H11A	119.7
N2—Zr1—N4	80.10 (9)	C13—C12—C11	120.2 (4)
N1—Zr1—C34	88.49 (10)	C13—C12—H12A	119.9
N2—Zr1—C34	143.15 (10)	C11—C12—H12A	119.9
N4—Zr1—C34	129.52 (11)	C12—C13—C14	120.0 (4)
N1—Zr1—C35	84.59 (10)	C12—C13—H13A	120.0
N2—Zr1—C35	142.10 (10)	C14—C13—H13A	120.0
N4—Zr1—C35	133.95 (10)	C13—C14—C15	120.4 (4)
C34—Zr1—C35	32.61 (11)	C13—C14—H14A	119.8
N1—Zr1—C33	119.47 (11)	C15—C14—H14A	119.8
N2—Zr1—C33	154.74 (10)	C10—C15—C14	119.7 (4)
N4—Zr1—C33	97.16 (10)	C10—C15—H15A	120.2
C34—Zr1—C33	32.37 (11)	C14—C15—H15A	120.2
C35—Zr1—C33	53.48 (11)	Si1—C16—H16A	109.5
N1—Zr1—Cl2	89.79 (7)	Si1—C16—H16B	109.5
N2—Zr1—Cl2	80.36 (6)	H16A—C16—H16B	109.5
N4—Zr1—Cl2	81.87 (6)	Si1—C16—H16C	109.5
C34—Zr1—Cl2	120.44 (9)	H16A—C16—H16C	109.5
C35—Zr1—Cl2	88.01 (8)	H16B—C16—H16C	109.5
C33—Zr1—Cl2	124.38 (8)	Si1—C17—H17A	109.5
N1—Zr1—C37	137.10 (10)	Si1—C17—H17B	109.5
N2—Zr1—C37	162.75 (9)	H17A—C17—H17B	109.5
N4—Zr1—C37	82.98 (10)	Si1—C17—H17C	109.5
C34—Zr1—C37	53.26 (11)	H17A—C17—H17C	109.5
C35—Zr1—C37	52.94 (11)	H17B—C17—H17C	109.5
C33—Zr1—C37	32.02 (11)	C19—C18—C23	121.8 (3)
Cl2—Zr1—C37	93.98 (8)	C19—C18—N3	119.4 (3)
N1—Zr1—C36	111.93 (10)	C23—C18—N3	118.7 (3)
N2—Zr1—C36	152.26 (10)	C18—C19—C20	117.6 (3)
N4—Zr1—C36	103.14 (10)	C18—C19—C24	124.0 (3)
C34—Zr1—C36	53.18 (11)	C20—C19—C24	118.4 (3)
C35—Zr1—C36	31.75 (11)	C21—C20—C19	121.1 (3)
C33—Zr1—C36	52.94 (11)	C21—C20—H20A	119.5
Cl2—Zr1—C36	72.98 (8)	C19—C20—H20A	119.5
C37—Zr1—C36	31.79 (11)	C20—C21—C22	120.8 (3)
N1—Zr1—Cl1	88.80 (7)	C20—C21—H21A	119.6
N2—Zr1—Cl1	79.85 (6)	C22—C21—H21A	119.6
N4—Zr1—Cl1	84.96 (6)	C21—C22—C23	120.3 (4)
C34—Zr1—Cl1	81.65 (9)	C21—C22—H22A	119.8
C35—Zr1—Cl1	113.88 (8)	C23—C22—H22A	119.8
C33—Zr1—Cl1	74.90 (8)	C18—C23—C22	118.3 (3)
Cl2—Zr1—Cl1	157.82 (3)	C18—C23—C25	122.9 (3)
C37—Zr1—Cl1	102.06 (8)	C22—C23—C25	118.8 (3)
C36—Zr1—Cl1	127.71 (8)	C19—C24—H24A	109.5
N1—Zr1—C9	30.03 (9)	C19—C24—H24B	109.5
N2—Zr1—C9	29.63 (8)	H24A—C24—H24B	109.5
N4—Zr1—C9	109.73 (9)	C19—C24—H24C	109.5
C34—Zr1—C9	116.25 (10)	H24A—C24—H24C	109.5
C35—Zr1—C9	114.06 (10)	H24B—C24—H24C	109.5
C33—Zr1—C9	142.91 (10)	C23—C25—H25A	109.5
Cl2—Zr1—C9	85.40 (6)	C23—C25—H25B	109.5
C37—Zr1—C9	166.99 (10)	H25A—C25—H25B	109.5
C36—Zr1—C9	137.36 (10)	C23—C25—H25C	109.5
Cl1—Zr1—C9	82.35 (6)	H25A—C25—H25C	109.5
N2—Si1—N3	103.52 (11)	H25B—C25—H25C	109.5
N2—Si1—C17	111.54 (13)	N4—C26—N3	123.0 (3)
N3—Si1—C17	108.83 (13)	N4—C26—C27	117.3 (3)
N2—Si1—C16	115.46 (14)	N3—C26—C27	119.6 (2)
N3—Si1—C16	108.36 (13)	C32—C27—C28	119.3 (3)
C17—Si1—C16	108.82 (15)	C32—C27—C26	119.3 (3)
C9—N1—C1	121.6 (2)	C28—C27—C26	121.1 (3)
C9—N1—Zr1	93.77 (17)	C27—C28—C29	120.2 (3)
C1—N1—Zr1	144.60 (19)	C27—C28—H28A	119.9
C9—N2—Si1	135.7 (2)	C29—C28—H28A	119.9
C9—N2—Zr1	93.08 (17)	C30—C29—C28	120.3 (4)
Si1—N2—Zr1	130.28 (13)	C30—C29—H29A	119.8
C26—N3—C18	118.4 (2)	C28—C29—H29A	119.8
C26—N3—Si1	124.02 (19)	C29—C30—C31	119.5 (3)
C18—N3—Si1	116.92 (19)	C29—C30—H30A	120.3
C26—N4—Zr1	133.0 (2)	C31—C30—H30A	120.3
C26—N4—H4A	113.5	C30—C31—C32	120.8 (4)
Zr1—N4—H4A	113.5	C30—C31—H31A	119.6
C6—C1—C2	120.8 (3)	C32—C31—H31A	119.6
C6—C1—N1	120.4 (3)	C27—C32—C31	119.8 (4)
C2—C1—N1	118.8 (3)	C27—C32—H32A	120.1
C3—C2—C1	118.4 (4)	C31—C32—H32A	120.1
C3—C2—C7	119.4 (4)	C37—C33—C34	107.8 (3)
C1—C2—C7	122.2 (3)	C37—C33—Zr1	74.68 (19)
C4—C3—C2	121.2 (4)	C34—C33—Zr1	72.90 (19)
C4—C3—H3A	119.4	C37—C33—H33A	125.8
C2—C3—H3A	119.4	C34—C33—H33A	125.8
C5—C4—C3	119.8 (4)	Zr1—C33—H33A	125.8
C5—C4—H4B	120.1	C33—C34—C35	107.6 (3)
C3—C4—H4B	120.1	C33—C34—Zr1	74.73 (18)
C4—C5—C6	121.6 (4)	C35—C34—Zr1	74.18 (18)
C4—C5—H5A	119.2	C33—C34—H34A	125.7
C6—C5—H5A	119.2	C35—C34—H34A	125.7
C1—C6—C5	118.2 (4)	Zr1—C34—H34A	125.7
C1—C6—C8	122.5 (3)	C36—C35—C34	108.2 (3)
C5—C6—C8	119.3 (4)	C36—C35—Zr1	75.81 (18)
C2—C7—H7A	109.5	C34—C35—Zr1	73.21 (18)
C2—C7—H7B	109.5	C36—C35—H35A	125.5
H7A—C7—H7B	109.5	C34—C35—H35A	125.5
C2—C7—H7C	109.5	Zr1—C35—H35A	125.5
H7A—C7—H7C	109.5	C35—C36—C37	108.1 (3)
H7B—C7—H7C	109.5	C35—C36—Zr1	72.43 (18)
C6—C8—H8A	109.5	C37—C36—Zr1	73.54 (18)
C6—C8—H8B	109.5	C35—C36—H36A	125.7
H8A—C8—H8B	109.5	C37—C36—H36A	125.7
C6—C8—H8C	109.5	Zr1—C36—H36A	125.7
H8A—C8—H8C	109.5	C36—C37—C33	108.3 (3)
H8B—C8—H8C	109.5	C36—C37—Zr1	74.66 (18)
N2—C9—N1	113.4 (3)	C33—C37—Zr1	73.30 (18)
N2—C9—C10	123.3 (3)	C36—C37—H37A	125.5
N1—C9—C10	123.3 (3)	C33—C37—H37A	125.5
N2—C9—Zr1	57.29 (15)	Zr1—C37—H37A	125.5
N1—C9—Zr1	56.21 (15)	Cl4—C38—Cl3	112.5 (3)
C10—C9—Zr1	176.7 (2)	Cl4—C38—H38A	109.1
C11—C10—C15	119.0 (3)	Cl3—C38—H38A	109.1
C11—C10—C9	121.2 (3)	Cl4—C38—H38B	109.1
C15—C10—C9	119.8 (3)	Cl3—C38—H38B	109.1
C10—C11—C12	120.6 (4)	H38A—C38—H38B	107.8