trans-Di­chloro-cis-bis(3,6-di­methyl­carbazolyl)-cis-bis­(tetra­hydro­furan)­zirconium(IV) benzene sesquisolvate

In the title compound, [ZrCl₂(C₁₄H₁₂N)₂(C₄H₈O)₂]·1.5C₆H₆, the Zr atom is pseudo-octahedral, with two Cl atoms in trans positions and two tetra­hydro­furan mol­ecules in cis positions. The two 3,6-di­methyl­carbazolyl ligands are in cis positions and are canted with respect to one another. The two Zr-N distances are 2.1148 (18) and 2.1236 (18) Å, and the N-Zr-N angle is 95.08 (7)°. The title compound crystallizes as the benzene solvate, with one of the benzene mol­ecules positioned on an inversion center.

S1. Comment

Amide complexes of transition metals are known to display interesting reactivity that is often unusual. This fact has been highlighted recently by the reduction of N₂ to NH₃, using a tris amide complex of Mo, by Schrock and co-workers (Yandulov et al., 2002, 2003). The accomplishment of one of the holy grails of inorganic chemistry is the culmination of the application of the electronic properties of hard amide ligands, an area that has been reviewed recently (Cummins, 1998; Schrock, 1997a,b). In contrast to these hard electronic ligands, recent work by ourselves (Nygren et al., 2003a,b) and others (Riley et al., 1998, 1999, 2001; Tanski & Parkin, 2003) has been based on the exploration of the chemistry of amide ligands in which the π interaction is uncertain with respect to the donation to the metal center. These amides with a lower π basicity (Tanski & Parkin, 2003) form a class of non-innocent ligands in coordination chemistry that differ from the non-innocent ligands described by Gray et al. (1967) in that the oxidation state is not uncertain, only the degree of electronic coupling between the π-donating ligating atom and the metal center. Although formally an LX ligand (Green, 1995), we note that the carbazolyl ligand is related to the N-heterocyclic carbenes (Tulloch et al., 2003; Arduengo, 1999; Herrmann, 2002), which are known to be almost pure σ donors, though in the case of carbazolyl, there is some π basicity. In this structure report, we describe a neutral bis-carbazolyl zirconium dichloride that will serve as a useful synthetic entrance into this area.

Carbazolyl complexes of transition metals that are σ-bound are rare (Lopez et al., 2002); most of the known examples (Riley et al., 1998, 1999, 2001) involve group 4B and 5B metals. A few bis-carbazolyl structures are known for the group 4B metals, most of which contain titanium (Riley et al., 2001). There are also a few known complexes for the group 5B metals (Riley et al., 1999).

Recently, the crystal structures of (tetrahydrofuran)potassium mer-[tris(carbazolyl)-trans-dichloro-(tetrahydrofurano)zirconate] and the tetrakis-(tetrahydrofurano)lithium mer-[tris(carbazolyl)-trans-dichloro-(tetrahydrofurano)zirconate] have been reported. (Nygren et al., 2003a,b).

The molecular structure of (I) is shown in Fig. 1 and consists of a pseudo-octahedral zirconium center bearing trans chloro ligands, cis carbazolyl moieties and cis-coordinated tetrahydrofuran molecules. Examination of the Cambridge Structural Database (Allen, 2002; Bruno et al., 2002) reveals that this composition of the first coordination sphere, consisting of two N atoms, two O atoms and two chloro ligands, is quite common for the group 4B metals, and all bond lengths and angles of the title structure are typical of those observed in zirconium complexes.

Examination of the intermolecular correlations reveals several interactions that are shorter than the sum of the van der Waals radii. Interestingly, the benzene molecules located at the cell corners do not show any of these short contacts, whereas the internal benzene molecules bridge between the carbazolyl of one molecule and the thf molecule coordinated to the Zr atom in another, using atoms H10, C38 and H35A. Another long-range interaction pairs two molecules together through mutually cis interactions between atoms Cl2 and H27B. Although this does not constitute a strongly bonded dimer, the pairs of these molecules then interact through shorter-range interactions between the coordinated thf and the mutually cis aromatic systems of the carbazolyl moieties. A similar structural disposition is seen in the tetrakis(tetrahydrofurano)lithium mer-[tris(carbazolyl)-trans-dichloro]tetrahydrofurano)zirconate (Nygren et al., 2003a). The final set of interactions occur between the methyl group (C14) and the aromatic ring of the neighboring molecule (atoms C21 and C26). The opposite methyl group on the same carbazolyl ligand has a strong interaction with a carbazolyl ligand on a different zirconium center of a neighboring molecule [2.7420 (14) Å; Allen, 2002; Bruno et al., 2002]. The range of distances for the intermolecular interactions is approximately 2.372–3.811 Å (Allen, 2002; Bruno et al., 2002). Thus a zigzag chain is formed in the bc plane throughout the extended lattice.

S2. Experimental

Dropwise addition of dry tetrahydrofuran to a mixture of ZrCl₄(s) (0.43 g, 0.0018 mol) and previously prepared carbazolyl tetrahydrofuran lithium(s) (1.01 g, 0.0037 mol) at 195 K, resulted in a slow reaction that, on warming to room temperature, afforded an orange–yellow solution. After filtration, tetrahydrofuran was evacuated and the product was washed with pentane. Benzene was added to the compound and large orange–yellow block-like crystals formed spontaneously at room temperature over a period of one week. This compound has been characterized by one- and two-dimensional ¹H and ¹³C NMR spectroscopy at variable temperature in solution. The spectroscopic data fully support formation of this compound.

S3. Refinement

All H atoms were introduced at calculated positions and treated using a riding model [U_iso(H)=1.2U_eq(C), C—H (CH₃) = 0.98 Å, C—H (CH₂) = 0.99 Å and C—H (aromatic CH) = 0.95 Å].

Computing details

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

Figures

	Fig. 1. A view of the structure of (I), showing the atomic numbering. All H atoms and solvent molecules have been omitted for clarity. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I), viewed along a. All H atoms have been omitted for clarity.

trans-dichloro-cis-Bis(3,6-dimethylcarbazolyl)-cis- bis(tetrahydrofuran)zirconium(IV) benzene sesquisolvate

Crystal data

[ZrCl2(C14H12N)2(C4H8O)2]·1.5C6H6	F(000) = 1692
Mr = 811.98	Dx = 1.342 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 21512 reflections
a = 10.200 (3) Å	θ = 2.3–26.5°
b = 17.594 (5) Å	µ = 0.45 mm^−1
c = 22.760 (7) Å	T = 173 K
β = 100.200 (5)°	Fragment, yellow
V = 4020 (2) Å^3	0.30 × 0.18 × 0.17 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer	8342 independent reflections
Radiation source: fine-focus sealed tube	6645 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.041
Detector resolution: not measured pixels mm^-1	θmax = 26.5°, θmin = 1.5°
ϕ and ω scans	h = −12→12
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −22→22
Tmin = 0.891, Tmax = 0.927	l = −28→28
39916 measured reflections

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.085	H-atom parameters constrained
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0347P)^2 + 2.6992P] where P = (Fo^2 + 2Fc^2)/3
8342 reflections	(Δ/σ)max = 0.041
473 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.31 e Å^−3

Special details

Experimental. Data were collected using a Bruker AXS SMART 1000 diffractometer equipped with a CCD area detector and graphite monochromated Mo source operating with a Nicolet liquid nitrogen cooling system at 173 K. Data were measured using phi–omega scans of 0.3 degrees with an integration time of 20 s. A total of 2424 frames were collected, with the initial 606 frames recollected in the final run.

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
C1	0.4659 (2)	0.89192 (12)	0.17262 (10)	0.0214 (4)
C2	0.3716 (2)	0.91914 (12)	0.12549 (10)	0.0251 (5)
H2	0.2882	0.9381	0.1321	0.030*
C3	0.4029 (2)	0.91778 (13)	0.06851 (10)	0.0276 (5)
H3	0.3394	0.9366	0.0362	0.033*
C4	0.5245 (2)	0.88976 (13)	0.05682 (10)	0.0287 (5)
C5	0.6154 (2)	0.86063 (13)	0.10413 (10)	0.0271 (5)
H5	0.6973	0.8400	0.0971	0.033*
C6	0.5870 (2)	0.86146 (12)	0.16182 (10)	0.0233 (5)
C7	0.6631 (2)	0.83996 (12)	0.21919 (10)	0.0226 (5)
C8	0.7902 (2)	0.80943 (13)	0.23657 (11)	0.0262 (5)
H8	0.8423	0.7965	0.2073	0.031*
C9	0.8402 (2)	0.79805 (13)	0.29644 (11)	0.0277 (5)
C10	0.7606 (2)	0.81740 (14)	0.33812 (11)	0.0294 (5)
H10	0.7950	0.8097	0.3793	0.035*
C11	0.6339 (2)	0.84737 (13)	0.32218 (10)	0.0280 (5)
H11	0.5817	0.8593	0.3516	0.034*
C12	0.5846 (2)	0.85954 (12)	0.26179 (10)	0.0226 (4)
C13	0.5543 (3)	0.89104 (15)	−0.00555 (11)	0.0361 (6)
H13A	0.6485	0.9035	−0.0041	0.043*
H13B	0.4986	0.9295	−0.0292	0.043*
H13C	0.5353	0.8410	−0.0240	0.043*
C14	0.9791 (2)	0.76743 (14)	0.31718 (12)	0.0328 (6)
H14A	1.0052	0.7360	0.2856	0.039*
H14B	0.9806	0.7365	0.3531	0.039*
H14C	1.0416	0.8099	0.3263	0.039*
C15	0.3208 (2)	0.84825 (12)	0.40328 (9)	0.0205 (4)
C16	0.3361 (2)	0.90844 (13)	0.44364 (10)	0.0243 (5)
H16	0.3453	0.9591	0.4305	0.029*
C17	0.3378 (2)	0.89278 (13)	0.50352 (10)	0.0279 (5)
H17	0.3496	0.9336	0.5313	0.033*
C18	0.3226 (2)	0.81894 (14)	0.52464 (10)	0.0282 (5)
C19	0.3059 (2)	0.75964 (13)	0.48401 (10)	0.0255 (5)
H19	0.2946	0.7092	0.4973	0.031*
C20	0.3054 (2)	0.77369 (12)	0.42376 (10)	0.0216 (4)
C21	0.2932 (2)	0.72475 (12)	0.37210 (9)	0.0212 (4)
C22	0.2707 (2)	0.64663 (12)	0.36406 (10)	0.0251 (5)
H22	0.2631	0.6154	0.3973	0.030*
C23	0.2593 (2)	0.61472 (12)	0.30770 (11)	0.0259 (5)
C24	0.2747 (2)	0.66227 (12)	0.26004 (10)	0.0250 (5)
H24	0.2694	0.6404	0.2215	0.030*
C25	0.2973 (2)	0.73980 (12)	0.26656 (10)	0.0227 (5)
H25	0.3080	0.7704	0.2334	0.027*
C26	0.3040 (2)	0.77174 (12)	0.32332 (9)	0.0201 (4)
C27	0.3247 (3)	0.80463 (16)	0.59030 (11)	0.0422 (7)
H27A	0.2368	0.8159	0.5999	0.051*
H27B	0.3916	0.8374	0.6140	0.051*
H27C	0.3469	0.7513	0.5995	0.051*
C28	0.2318 (3)	0.53096 (13)	0.29798 (12)	0.0369 (6)
H28A	0.2784	0.5023	0.3324	0.044*
H28B	0.2634	0.5144	0.2618	0.044*
H28C	0.1358	0.5217	0.2934	0.044*
C29	0.1924 (2)	1.08382 (15)	0.18600 (12)	0.0339 (6)
H29A	0.1592	1.1250	0.2091	0.041*
H29B	0.1191	1.0473	0.1730	0.041*
C30	0.2444 (3)	1.11541 (15)	0.13323 (12)	0.0367 (6)
H30A	0.1967	1.1626	0.1185	0.044*
H30B	0.2348	1.0780	0.1003	0.044*
C31	0.3895 (3)	1.1313 (2)	0.15750 (16)	0.0671 (11)
H31A	0.4455	1.1144	0.1286	0.081*
H31B	0.4035	1.1865	0.1645	0.081*
C32	0.4255 (3)	1.08971 (16)	0.21354 (12)	0.0393 (6)
H32A	0.4513	1.1255	0.2472	0.047*
H32B	0.5015	1.0553	0.2117	0.047*
C33	0.1831 (3)	1.08688 (14)	0.34367 (12)	0.0337 (6)
H33A	0.2282	1.1177	0.3168	0.040*
H33B	0.2328	1.0917	0.3850	0.040*
C34	0.0398 (3)	1.11117 (16)	0.33974 (13)	0.0438 (7)
H34A	−0.0017	1.1235	0.2981	0.053*
H34B	0.0324	1.1557	0.3655	0.053*
C35	−0.0231 (3)	1.04095 (16)	0.36210 (13)	0.0428 (7)
H35A	−0.0080	1.0398	0.4063	0.051*
H35B	−0.1201	1.0394	0.3467	0.051*
C36	0.0471 (2)	0.97537 (15)	0.33771 (12)	0.0333 (5)
H36A	0.0653	0.9340	0.3675	0.040*
H36B	−0.0080	0.9549	0.3009	0.040*
C37	0.1585 (3)	0.41791 (17)	0.02178 (13)	0.0465 (7)
H37	0.1521	0.4700	0.0318	0.056*
C38	0.0462 (3)	0.37257 (18)	0.01387 (13)	0.0468 (7)
H38	−0.0372	0.3935	0.0185	0.056*
C39	0.0552 (3)	0.29698 (18)	−0.00076 (13)	0.0476 (7)
H39	−0.0219	0.2657	−0.0061	0.057*
C40	0.1761 (3)	0.26690 (18)	−0.00755 (13)	0.0501 (7)
H40	0.1825	0.2148	−0.0177	0.060*
C41	0.2885 (3)	0.31253 (18)	0.00043 (13)	0.0483 (7)
H41	0.3720	0.2917	−0.0043	0.058*
C42	0.2794 (3)	0.38791 (17)	0.01514 (13)	0.0431 (7)
H42	0.3565	0.4192	0.0207	0.052*
C43	1.0435 (3)	0.5026 (3)	0.44678 (16)	0.0689 (11)
H43	1.0736	0.5044	0.4096	0.083*
C44	0.9926 (3)	0.4360 (2)	0.46506 (18)	0.0689 (10)
H44	0.9878	0.3919	0.4408	0.083*
C45	0.9491 (3)	0.4339 (2)	0.51847 (19)	0.0704 (10)
H45	0.9136	0.3881	0.5314	0.084*
Cl1	0.12403 (5)	0.89868 (3)	0.21157 (2)	0.02728 (13)
Cl2	0.48740 (6)	1.01537 (3)	0.34798 (3)	0.03082 (13)
N1	0.46165 (17)	0.89218 (10)	0.23456 (8)	0.0214 (4)
N2	0.31897 (17)	0.84922 (10)	0.34076 (8)	0.0203 (4)
O1	0.30721 (14)	1.04568 (8)	0.22171 (7)	0.0256 (3)
O2	0.17284 (15)	1.00721 (9)	0.32473 (7)	0.0273 (3)
Zr1	0.321098 (19)	0.941763 (11)	0.281043 (9)	0.01926 (6)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0220 (11)	0.0201 (10)	0.0222 (11)	−0.0017 (8)	0.0044 (9)	0.0002 (8)
C2	0.0243 (11)	0.0255 (11)	0.0245 (12)	0.0019 (9)	0.0019 (9)	0.0003 (9)
C3	0.0309 (12)	0.0272 (12)	0.0225 (12)	−0.0015 (9)	−0.0013 (10)	0.0006 (9)
C4	0.0357 (13)	0.0266 (12)	0.0247 (12)	−0.0041 (10)	0.0075 (10)	−0.0027 (9)
C5	0.0262 (12)	0.0307 (12)	0.0259 (12)	−0.0011 (9)	0.0086 (10)	−0.0037 (10)
C6	0.0218 (11)	0.0221 (11)	0.0257 (12)	−0.0017 (8)	0.0039 (9)	−0.0014 (9)
C7	0.0205 (11)	0.0222 (10)	0.0257 (11)	−0.0014 (8)	0.0055 (9)	−0.0026 (9)
C8	0.0210 (11)	0.0277 (12)	0.0311 (12)	0.0005 (9)	0.0080 (9)	−0.0010 (10)
C9	0.0190 (11)	0.0272 (12)	0.0358 (13)	−0.0002 (9)	0.0014 (10)	0.0013 (10)
C10	0.0236 (12)	0.0380 (13)	0.0249 (12)	0.0053 (10)	−0.0002 (9)	0.0039 (10)
C11	0.0226 (11)	0.0374 (13)	0.0244 (12)	0.0046 (10)	0.0055 (9)	0.0025 (10)
C12	0.0183 (10)	0.0232 (11)	0.0264 (12)	0.0006 (8)	0.0039 (9)	0.0014 (9)
C13	0.0433 (15)	0.0420 (15)	0.0238 (13)	0.0006 (12)	0.0082 (11)	0.0019 (11)
C14	0.0209 (12)	0.0348 (13)	0.0415 (15)	0.0021 (10)	0.0024 (10)	0.0010 (11)
C15	0.0159 (10)	0.0258 (11)	0.0195 (11)	0.0043 (8)	0.0024 (8)	0.0037 (8)
C16	0.0252 (11)	0.0222 (11)	0.0249 (12)	0.0024 (9)	0.0027 (9)	−0.0005 (9)
C17	0.0307 (12)	0.0296 (12)	0.0232 (12)	0.0029 (10)	0.0044 (10)	−0.0041 (9)
C18	0.0284 (12)	0.0337 (13)	0.0227 (12)	0.0038 (10)	0.0050 (10)	0.0031 (10)
C19	0.0269 (12)	0.0245 (11)	0.0251 (12)	0.0016 (9)	0.0043 (9)	0.0052 (9)
C20	0.0169 (10)	0.0250 (11)	0.0225 (11)	0.0027 (8)	0.0021 (8)	0.0012 (9)
C21	0.0157 (10)	0.0247 (11)	0.0229 (11)	0.0031 (8)	0.0021 (8)	0.0014 (9)
C22	0.0224 (11)	0.0240 (11)	0.0282 (12)	0.0006 (9)	0.0030 (9)	0.0040 (9)
C23	0.0209 (11)	0.0226 (11)	0.0332 (13)	0.0010 (9)	0.0022 (9)	−0.0006 (10)
C24	0.0220 (11)	0.0273 (11)	0.0248 (12)	0.0015 (9)	0.0016 (9)	−0.0057 (9)
C25	0.0193 (11)	0.0254 (11)	0.0233 (11)	0.0026 (8)	0.0037 (9)	0.0014 (9)
C26	0.0149 (10)	0.0221 (10)	0.0229 (11)	0.0027 (8)	0.0024 (8)	0.0003 (9)
C27	0.0611 (18)	0.0423 (15)	0.0235 (13)	−0.0036 (13)	0.0090 (12)	0.0013 (11)
C28	0.0442 (15)	0.0246 (12)	0.0413 (15)	−0.0023 (11)	0.0061 (12)	−0.0040 (11)
C29	0.0248 (12)	0.0373 (13)	0.0386 (14)	0.0075 (10)	0.0031 (11)	0.0148 (11)
C30	0.0373 (14)	0.0364 (14)	0.0361 (14)	0.0039 (11)	0.0060 (11)	0.0119 (11)
C31	0.0372 (16)	0.088 (3)	0.073 (2)	−0.0141 (16)	0.0012 (16)	0.051 (2)
C32	0.0313 (13)	0.0438 (15)	0.0417 (15)	−0.0153 (11)	0.0038 (11)	0.0121 (12)
C33	0.0402 (14)	0.0283 (12)	0.0329 (13)	0.0035 (10)	0.0070 (11)	−0.0067 (10)
C34	0.0448 (16)	0.0405 (15)	0.0483 (17)	0.0134 (12)	0.0143 (13)	−0.0057 (13)
C35	0.0374 (15)	0.0528 (17)	0.0417 (16)	0.0088 (12)	0.0166 (12)	−0.0041 (13)
C36	0.0257 (12)	0.0387 (14)	0.0380 (14)	0.0026 (10)	0.0126 (11)	0.0028 (11)
C37	0.0533 (18)	0.0428 (16)	0.0448 (17)	0.0076 (13)	0.0131 (14)	0.0043 (13)
C38	0.0357 (15)	0.066 (2)	0.0393 (16)	0.0151 (14)	0.0075 (12)	0.0078 (14)
C39	0.0393 (16)	0.064 (2)	0.0387 (16)	−0.0057 (14)	0.0034 (13)	−0.0033 (14)
C40	0.0544 (19)	0.0488 (17)	0.0486 (18)	0.0001 (14)	0.0134 (15)	−0.0085 (14)
C41	0.0395 (16)	0.0604 (19)	0.0482 (18)	0.0111 (14)	0.0161 (13)	0.0065 (15)
C42	0.0395 (15)	0.0484 (17)	0.0418 (16)	−0.0012 (13)	0.0081 (12)	0.0092 (13)
C43	0.047 (2)	0.108 (3)	0.050 (2)	0.010 (2)	0.0056 (16)	0.016 (2)
C44	0.050 (2)	0.084 (3)	0.066 (2)	0.0049 (19)	−0.0075 (18)	−0.010 (2)
C45	0.049 (2)	0.080 (3)	0.078 (3)	−0.0065 (18)	0.0012 (19)	0.016 (2)
Cl1	0.0217 (3)	0.0323 (3)	0.0266 (3)	−0.0023 (2)	0.0007 (2)	0.0017 (2)
Cl2	0.0288 (3)	0.0331 (3)	0.0285 (3)	−0.0054 (2)	−0.0007 (2)	−0.0019 (2)
N1	0.0195 (9)	0.0238 (9)	0.0207 (9)	0.0022 (7)	0.0028 (7)	0.0017 (7)
N2	0.0203 (9)	0.0216 (9)	0.0189 (9)	0.0016 (7)	0.0029 (7)	0.0000 (7)
O1	0.0201 (8)	0.0269 (8)	0.0299 (9)	−0.0007 (6)	0.0046 (6)	0.0072 (7)
O2	0.0263 (8)	0.0257 (8)	0.0312 (9)	0.0023 (6)	0.0086 (7)	−0.0018 (7)
Zr1	0.01721 (11)	0.02080 (11)	0.01970 (11)	0.00123 (8)	0.00307 (8)	0.00188 (8)

Geometric parameters (Å, º)

C1—C2	1.393 (3)	C28—H28A	0.9800
C1—C6	1.407 (3)	C28—H28B	0.9800
C1—N1	1.418 (3)	C28—H28C	0.9800
C2—C3	1.389 (3)	C29—O1	1.465 (3)
C2—H2	0.9500	C29—C30	1.503 (3)
C3—C4	1.404 (3)	C29—H29A	0.9900
C3—H3	0.9500	C29—H29B	0.9900
C4—C5	1.388 (3)	C30—C31	1.511 (4)
C4—C13	1.504 (3)	C30—H30A	0.9900
C5—C6	1.394 (3)	C30—H30B	0.9900
C5—H5	0.9500	C31—C32	1.460 (4)
C6—C7	1.446 (3)	C31—H31A	0.9900
C7—C8	1.394 (3)	C31—H31B	0.9900
C7—C12	1.405 (3)	C32—O1	1.473 (3)
C8—C9	1.382 (3)	C32—H32A	0.9900
C8—H8	0.9500	C32—H32B	0.9900
C9—C10	1.395 (3)	C33—O2	1.465 (3)
C9—C14	1.512 (3)	C33—C34	1.511 (4)
C10—C11	1.384 (3)	C33—H33A	0.9900
C10—H10	0.9500	C33—H33B	0.9900
C11—C12	1.394 (3)	C34—C35	1.521 (4)
C11—H11	0.9500	C34—H34A	0.9900
C12—N1	1.419 (3)	C34—H34B	0.9900
C13—H13A	0.9800	C35—C36	1.514 (3)
C13—H13B	0.9800	C35—H35A	0.9900
C13—H13C	0.9800	C35—H35B	0.9900
C14—H14A	0.9800	C36—O2	1.477 (3)
C14—H14B	0.9800	C36—H36A	0.9900
C14—H14C	0.9800	C36—H36B	0.9900
C15—C16	1.392 (3)	C37—C42	1.374 (4)
C15—C20	1.410 (3)	C37—C38	1.381 (4)
C15—N2	1.420 (3)	C37—H37	0.9500
C16—C17	1.388 (3)	C38—C39	1.378 (4)
C16—H16	0.9500	C38—H38	0.9500
C17—C18	1.403 (3)	C39—C40	1.376 (4)
C17—H17	0.9500	C39—H39	0.9500
C18—C19	1.385 (3)	C40—C41	1.385 (4)
C18—C27	1.512 (3)	C40—H40	0.9500
C19—C20	1.392 (3)	C41—C42	1.375 (4)
C19—H19	0.9500	C41—H41	0.9500
C20—C21	1.445 (3)	C42—H42	0.9500
C21—C22	1.400 (3)	C43—C45^i	1.364 (6)
C21—C26	1.404 (3)	C43—C44	1.375 (5)
C22—C23	1.386 (3)	C43—H43	0.9500
C22—H22	0.9500	C44—C45	1.366 (5)
C23—C24	1.401 (3)	C44—H44	0.9500
C23—C28	1.509 (3)	C45—C43^i	1.364 (6)
C24—C25	1.387 (3)	C45—H45	0.9500
C24—H24	0.9500	Cl1—Zr1	2.4473 (7)
C25—C26	1.399 (3)	Cl2—Zr1	2.4413 (7)
C25—H25	0.9500	N1—Zr1	2.1148 (18)
C26—N2	1.420 (3)	N2—Zr1	2.1236 (18)
C27—H27A	0.9800	O1—Zr1	2.2624 (15)
C27—H27B	0.9800	O2—Zr1	2.2659 (15)
C27—H27C	0.9800
C2—C1—C6	120.3 (2)	O1—C29—H29B	110.8
C2—C1—N1	128.8 (2)	C30—C29—H29B	110.8
C6—C1—N1	110.93 (18)	H29A—C29—H29B	108.9
C3—C2—C1	118.1 (2)	C29—C30—C31	103.7 (2)
C3—C2—H2	120.9	C29—C30—H30A	111.0
C1—C2—H2	120.9	C31—C30—H30A	111.0
C2—C3—C4	122.7 (2)	C29—C30—H30B	111.0
C2—C3—H3	118.7	C31—C30—H30B	111.0
C4—C3—H3	118.7	H30A—C30—H30B	109.0
C5—C4—C3	118.3 (2)	C32—C31—C30	107.8 (2)
C5—C4—C13	121.3 (2)	C32—C31—H31A	110.1
C3—C4—C13	120.5 (2)	C30—C31—H31A	110.1
C4—C5—C6	120.3 (2)	C32—C31—H31B	110.1
C4—C5—H5	119.8	C30—C31—H31B	110.1
C6—C5—H5	119.8	H31A—C31—H31B	108.5
C5—C6—C1	120.3 (2)	C31—C32—O1	106.8 (2)
C5—C6—C7	132.8 (2)	C31—C32—H32A	110.4
C1—C6—C7	106.80 (19)	O1—C32—H32A	110.4
C8—C7—C12	120.9 (2)	C31—C32—H32B	110.4
C8—C7—C6	132.9 (2)	O1—C32—H32B	110.4
C12—C7—C6	106.19 (19)	H32A—C32—H32B	108.6
C9—C8—C7	119.8 (2)	O2—C33—C34	103.6 (2)
C9—C8—H8	120.1	O2—C33—H33A	111.0
C7—C8—H8	120.1	C34—C33—H33A	111.0
C8—C9—C10	118.5 (2)	O2—C33—H33B	111.0
C8—C9—C14	121.4 (2)	C34—C33—H33B	111.0
C10—C9—C14	120.0 (2)	H33A—C33—H33B	109.0
C11—C10—C9	122.9 (2)	C33—C34—C35	102.2 (2)
C11—C10—H10	118.5	C33—C34—H34A	111.3
C9—C10—H10	118.5	C35—C34—H34A	111.3
C10—C11—C12	118.3 (2)	C33—C34—H34B	111.3
C10—C11—H11	120.9	C35—C34—H34B	111.3
C12—C11—H11	120.9	H34A—C34—H34B	109.2
C11—C12—C7	119.5 (2)	C36—C35—C34	104.0 (2)
C11—C12—N1	129.0 (2)	C36—C35—H35A	111.0
C7—C12—N1	111.44 (19)	C34—C35—H35A	111.0
C4—C13—H13A	109.5	C36—C35—H35B	111.0
C4—C13—H13B	109.5	C34—C35—H35B	111.0
H13A—C13—H13B	109.5	H35A—C35—H35B	109.0
C4—C13—H13C	109.5	O2—C36—C35	105.6 (2)
H13A—C13—H13C	109.5	O2—C36—H36A	110.6
H13B—C13—H13C	109.5	C35—C36—H36A	110.6
C9—C14—H14A	109.5	O2—C36—H36B	110.6
C9—C14—H14B	109.5	C35—C36—H36B	110.6
H14A—C14—H14B	109.5	H36A—C36—H36B	108.8
C9—C14—H14C	109.5	C42—C37—C38	120.2 (3)
H14A—C14—H14C	109.5	C42—C37—H37	119.9
H14B—C14—H14C	109.5	C38—C37—H37	119.9
C16—C15—C20	119.7 (2)	C39—C38—C37	120.0 (3)
C16—C15—N2	129.20 (19)	C39—C38—H38	120.0
C20—C15—N2	111.09 (18)	C37—C38—H38	120.0
C17—C16—C15	118.5 (2)	C40—C39—C38	119.9 (3)
C17—C16—H16	120.7	C40—C39—H39	120.1
C15—C16—H16	120.7	C38—C39—H39	120.1
C16—C17—C18	122.5 (2)	C39—C40—C41	120.0 (3)
C16—C17—H17	118.8	C39—C40—H40	120.0
C18—C17—H17	118.8	C41—C40—H40	120.0
C19—C18—C17	118.5 (2)	C42—C41—C40	120.0 (3)
C19—C18—C27	120.9 (2)	C42—C41—H41	120.0
C17—C18—C27	120.6 (2)	C40—C41—H41	120.0
C18—C19—C20	120.2 (2)	C37—C42—C41	119.9 (3)
C18—C19—H19	119.9	C37—C42—H42	120.0
C20—C19—H19	119.9	C41—C42—H42	120.0
C19—C20—C15	120.6 (2)	C45^i—C43—C44	120.5 (4)
C19—C20—C21	132.9 (2)	C45^i—C43—H43	119.7
C15—C20—C21	106.50 (19)	C44—C43—H43	119.7
C22—C21—C26	120.6 (2)	C45—C44—C43	119.5 (4)
C22—C21—C20	132.8 (2)	C45—C44—H44	120.3
C26—C21—C20	106.56 (19)	C43—C44—H44	120.3
C23—C22—C21	120.2 (2)	C43^i—C45—C44	120.0 (4)
C23—C22—H22	119.9	C43^i—C45—H45	120.0
C21—C22—H22	119.9	C44—C45—H45	120.0
C22—C23—C24	118.2 (2)	C1—N1—C12	104.63 (17)
C22—C23—C28	120.9 (2)	C1—N1—Zr1	129.90 (14)
C24—C23—C28	120.9 (2)	C12—N1—Zr1	125.02 (14)
C25—C24—C23	122.9 (2)	C15—N2—C26	104.50 (16)
C25—C24—H24	118.5	C15—N2—Zr1	130.60 (14)
C23—C24—H24	118.5	C26—N2—Zr1	124.73 (14)
C24—C25—C26	118.3 (2)	C29—O1—C32	106.36 (17)
C24—C25—H25	120.9	C29—O1—Zr1	131.35 (13)
C26—C25—H25	120.9	C32—O1—Zr1	122.28 (14)
C25—C26—C21	119.7 (2)	C33—O2—C36	108.89 (17)
C25—C26—N2	128.95 (19)	C33—O2—Zr1	126.65 (14)
C21—C26—N2	111.33 (18)	C36—O2—Zr1	124.46 (13)
C18—C27—H27A	109.5	N1—Zr1—N2	95.08 (7)
C18—C27—H27B	109.5	N1—Zr1—O1	90.64 (6)
H27A—C27—H27B	109.5	N2—Zr1—O1	174.27 (6)
C18—C27—H27C	109.5	N1—Zr1—O2	173.40 (6)
H27A—C27—H27C	109.5	N2—Zr1—O2	91.46 (6)
H27B—C27—H27C	109.5	O1—Zr1—O2	82.83 (6)
C23—C28—H28A	109.5	N1—Zr1—Cl2	94.21 (5)
C23—C28—H28B	109.5	N2—Zr1—Cl2	95.28 (5)
H28A—C28—H28B	109.5	O1—Zr1—Cl2	84.66 (5)
C23—C28—H28C	109.5	O2—Zr1—Cl2	84.29 (5)
H28A—C28—H28C	109.5	N1—Zr1—Cl1	95.80 (5)
H28B—C28—H28C	109.5	N2—Zr1—Cl1	94.34 (5)
O1—C29—C30	104.60 (19)	O1—Zr1—Cl1	84.68 (4)
O1—C29—H29A	110.8	O2—Zr1—Cl1	84.57 (5)
C30—C29—H29A	110.8	Cl2—Zr1—Cl1	165.44 (2)
C6—C1—C2—C3	−2.3 (3)	C34—C35—C36—O2	21.0 (3)
N1—C1—C2—C3	175.1 (2)	C42—C37—C38—C39	0.0 (4)
C1—C2—C3—C4	0.5 (3)	C37—C38—C39—C40	−0.1 (4)
C2—C3—C4—C5	1.6 (3)	C38—C39—C40—C41	0.1 (5)
C2—C3—C4—C13	−178.8 (2)	C39—C40—C41—C42	0.0 (5)
C3—C4—C5—C6	−1.8 (3)	C38—C37—C42—C41	0.2 (4)
C13—C4—C5—C6	178.6 (2)	C40—C41—C42—C37	−0.1 (4)
C4—C5—C6—C1	−0.1 (3)	C45^i—C43—C44—C45	0.1 (6)
C4—C5—C6—C7	−175.8 (2)	C43—C44—C45—C43^i	−0.1 (6)
C2—C1—C6—C5	2.2 (3)	C2—C1—N1—C12	−178.5 (2)
N1—C1—C6—C5	−175.72 (19)	C6—C1—N1—C12	−0.8 (2)
C2—C1—C6—C7	178.89 (19)	C2—C1—N1—Zr1	−6.0 (3)
N1—C1—C6—C7	1.0 (2)	C6—C1—N1—Zr1	171.64 (14)
C5—C6—C7—C8	−1.6 (4)	C11—C12—N1—C1	178.7 (2)
C1—C6—C7—C8	−177.7 (2)	C7—C12—N1—C1	0.3 (2)
C5—C6—C7—C12	175.4 (2)	C11—C12—N1—Zr1	5.7 (3)
C1—C6—C7—C12	−0.8 (2)	C7—C12—N1—Zr1	−172.65 (14)
C12—C7—C8—C9	0.1 (3)	C16—C15—N2—C26	178.5 (2)
C6—C7—C8—C9	176.7 (2)	C20—C15—N2—C26	−0.9 (2)
C7—C8—C9—C10	0.3 (3)	C16—C15—N2—Zr1	−6.2 (3)
C7—C8—C9—C14	−178.0 (2)	C20—C15—N2—Zr1	174.36 (14)
C8—C9—C10—C11	0.1 (4)	C25—C26—N2—C15	−179.4 (2)
C14—C9—C10—C11	178.4 (2)	C21—C26—N2—C15	1.6 (2)
C9—C10—C11—C12	−0.8 (4)	C25—C26—N2—Zr1	4.9 (3)
C10—C11—C12—C7	1.2 (3)	C21—C26—N2—Zr1	−174.09 (13)
C10—C11—C12—N1	−177.1 (2)	C30—C29—O1—C32	32.9 (3)
C8—C7—C12—C11	−0.9 (3)	C30—C29—O1—Zr1	−147.95 (16)
C6—C7—C12—C11	−178.2 (2)	C31—C32—O1—C29	−22.5 (3)
C8—C7—C12—N1	177.71 (19)	C31—C32—O1—Zr1	158.2 (2)
C6—C7—C12—N1	0.3 (2)	C34—C33—O2—C36	−26.5 (3)
C20—C15—C16—C17	0.9 (3)	C34—C33—O2—Zr1	152.48 (16)
N2—C15—C16—C17	−178.4 (2)	C35—C36—O2—C33	3.4 (3)
C15—C16—C17—C18	−0.9 (3)	C35—C36—O2—Zr1	−175.66 (15)
C16—C17—C18—C19	0.2 (4)	C1—N1—Zr1—N2	139.67 (18)
C16—C17—C18—C27	−179.8 (2)	C12—N1—Zr1—N2	−49.26 (17)
C17—C18—C19—C20	0.6 (3)	C1—N1—Zr1—O1	−39.95 (18)
C27—C18—C19—C20	−179.4 (2)	C12—N1—Zr1—O1	131.12 (16)
C18—C19—C20—C15	−0.5 (3)	C1—N1—Zr1—Cl2	−124.64 (17)
C18—C19—C20—C21	178.5 (2)	C12—N1—Zr1—Cl2	46.43 (16)
C16—C15—C20—C19	−0.2 (3)	C1—N1—Zr1—Cl1	44.77 (18)
N2—C15—C20—C19	179.26 (18)	C12—N1—Zr1—Cl1	−144.17 (16)
C16—C15—C20—C21	−179.47 (19)	C15—N2—Zr1—N1	136.55 (17)
N2—C15—C20—C21	0.0 (2)	C26—N2—Zr1—N1	−48.98 (16)
C19—C20—C21—C22	3.9 (4)	C15—N2—Zr1—O2	−42.56 (18)
C15—C20—C21—C22	−176.9 (2)	C26—N2—Zr1—O2	131.91 (16)
C19—C20—C21—C26	−178.2 (2)	C15—N2—Zr1—Cl2	41.84 (17)
C15—C20—C21—C26	0.9 (2)	C26—N2—Zr1—Cl2	−143.69 (15)
C26—C21—C22—C23	0.3 (3)	C15—N2—Zr1—Cl1	−127.22 (17)
C20—C21—C22—C23	177.9 (2)	C26—N2—Zr1—Cl1	47.25 (16)
C21—C22—C23—C24	1.8 (3)	C29—O1—Zr1—N1	126.9 (2)
C21—C22—C23—C28	−178.6 (2)	C32—O1—Zr1—N1	−54.14 (18)
C22—C23—C24—C25	−1.7 (3)	C29—O1—Zr1—O2	−54.07 (19)
C28—C23—C24—C25	178.6 (2)	C32—O1—Zr1—O2	124.93 (18)
C23—C24—C25—C26	−0.5 (3)	C29—O1—Zr1—Cl2	−138.97 (19)
C24—C25—C26—C21	2.6 (3)	C32—O1—Zr1—Cl2	40.03 (17)
C24—C25—C26—N2	−176.4 (2)	C29—O1—Zr1—Cl1	31.10 (19)
C22—C21—C26—C25	−2.5 (3)	C32—O1—Zr1—Cl1	−149.90 (18)
C20—C21—C26—C25	179.30 (18)	C33—O2—Zr1—N2	132.17 (17)
C22—C21—C26—N2	176.60 (18)	C36—O2—Zr1—N2	−48.97 (17)
C20—C21—C26—N2	−1.6 (2)	C33—O2—Zr1—O1	−48.30 (17)
O1—C29—C30—C31	−30.1 (3)	C36—O2—Zr1—O1	130.56 (17)
C29—C30—C31—C32	16.6 (4)	C33—O2—Zr1—Cl2	37.01 (17)
C30—C31—C32—O1	3.2 (4)	C36—O2—Zr1—Cl2	−144.13 (16)
O2—C33—C34—C35	38.7 (3)	C33—O2—Zr1—Cl1	−133.60 (17)
C33—C34—C35—C36	−36.7 (3)	C36—O2—Zr1—Cl1	45.26 (16)

Symmetry code: (i) −x+2, −y+1, −z+1.