(Tetra­hydro­furan)­potassium mer-trans-tris­(carbazolyl)­di­chloro(tetra­hydro­furan)­zirconate

In the title compound, [K(C₄H₈O)][ZrCl₂(C₁₂H₈N)₃(C₄H₈O)], the Zr atom is pseudo-octahedral, with two Cl ligands in trans positions. There is extensive interaction between the potassium cation and two of the aromatic carbazolyl ligands in η⁶ [C...K = 3.167 (3)–3.331 (3) Å] and η² [C...K = 3.147 (3)–3.268 (2) Å] fashions.

S1. Comment

Trisamido complexes of transition metals show a wide and varied reactivity, and the synthesis and exploration of this class of compounds has been the focus of considerable research in recent years in the inorganic community (Cummins et al., 1988; Cummins et al., 1991; (Cummins, 1998a; Schrock, 1997). The majority of these complexes contain hard electronic ligands (Cummins, 1998b). Recently, complexes with softer non-innocent ligands have been reported (Tanski & Parkin, 2003).

The electronic properties of the carbazolyl anion should predispose it to non-innocence when acting as a ligand at a transition metal center. Moreover, carbazolyl complexes of the transition metals that are σ-bound are rare (Lopez et al., 2002); most examples (Riley et al., 1998; Riley et al., 1999; Riley et al., 2001) are known for Groups IV and V. In this paper, brief details of the synthesis and full details of the structure of the first carbazolyl zirconium anion, mer-[tris(carbazolyl)-trans-dichloro- (tetrahydrofurano)zirconate] as the potassium thf adduct, (I), are reported. Examination of the Cambridge Structural Database (CSD; Allen & Motherwell, 2002; Bruno et al., 2002), revealed that the first coordination sphere, consisting of three N atoms, one O atom and two Cl atoms, is unique in the structural chemistry of zirconium.

The molecular structure of (I) is shown in Fig. 1. Examination of the CSD revealed that the Zr—N bond lengths [Zr—N_avg = 2.188 (17) Å] of the carbazolyl ligands are shorter than the mean Zr—N single bond (Zr—N_avg = 2.241 Å) reported in the literature, although they are not outside the range of the typical distances. The Zr—Cl bond lengths are well within the typical range of 2.379–2.776 Å (Allen & Motherwell, 2002; Bruno et al., 2002), though the Zr—Cl bond in (I) is slightly shorter than the mean of these distances, i.e. 2.514 Å [Zr—Cl1 = 2.4276 (7) Å and Zr—Cl2 = 2.4914 (6) Å].

There are two close interactions between the potassium cation and two of the carbazolyl ligands. One of the carbazolyl ligands is coordinated in an η⁶ fashion, and the average distance of this interaction is 3.264 Å. There is also an η² interaction with a carbazolyl ligand, in which the average distance is 3.198 Å. This type of close interaction between a transition metal anionic complex and the counter-ion is not uncommon. However, the fact that the crystallization from THF does not result in a coordination sphere composed solely of this ether, but rather one composed of a mixture of hard and soft bases (Pearson 1963, 1969), was surprising, given that K⁺ is considered a hard acid. The mixed nature of the coordination sphere prompted a further examination of the CSD. The search was based on all K⁺—arene interactions and revealed that potassium may coordinate in an η², η³ or η⁶ fashion, with a range of distances, over all hapticities, of 2.856–3.927 Å.

Given the mixed hard–soft coordination sphere, we chose to compare the structure with a soft ion of similar ionic radius and equal formal charge, namely Ag⁺, an archetypal soft acid. Surprisingly, very few Ag⁺—arene interactions were found. In the Pearson acid–base classification (Pearson 1963, 1969), K⁺ is a hard acid, whereas Ag⁺ is a soft acid; soft bases, such as arene π electron density, would be assumed to bind more strongly to the soft acid than to the hard acid. Moreover, Ag⁺ is used in chromatographic separations of alkenes and other unsaturated hydrocarbons (Williams & Mander, 2001) because of this interaction of Ag⁺ with the unsaturated π density, and several salts of Ag⁺ are soluble in aromatic hydrocarbons, in contrast to the K⁺ congeners. The dearth of structural data on arene—Ag⁺ and the number of arene—K⁺ interactions is therefore surprising. We speculate that the formally charge-separated nature of (I), and possibly the distribution of the negative charge in the carbazolyl portion of the anion, may play a role in ensuring that the observed structure is favorable. Theoretical and experimental studies are in progress to explore this possibility.

S2. Experimental

Treatment of a suspension of ZrCl₄ (2.32 g, 0.01 mol) in Et₂O, chilled to 195 K, with a freshly prepared concentrated tetrahydrofuran solution of carbazolyl potassium, formed by deprotonation of carbazole (5 g, 0.030 mol) with an excess of potassium hydride (2.4 g, 0.060 mol), resulted in a slow reaction that, on warming to room temperature, afforded a golden-yellow solution. Large leaf-like golden-yellow crystals of (I) grew spontaneously from the unstirred reaction mixture over a period of 3 d. The crystal growth occurred with precipitation of a quantity of bright-yellow powder. The latter gave identical spectroscopic data to the crystals. The compound has been characterized by one- and two-dimensional ¹H and ¹³C NMR spectroscopy at variable temperature in solution and CP-MAS ¹³C NMR in the solid state. The spectroscopic data fully support the formulation of (I) as [K(THF)][mer-(carbazolyl)₃ZrCl₂^.THF].

S3. Refinement

All H atoms were introduced at calculated positions and treated as riding [U_iso(H)=1.2U_eq(C) and C—H = 0.98 Å]. Friedel pairs were kept separate.

Computing details

Data collection: SMART (Bruker 1997); cell refinement: SAINT (Bruker 1997); 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 (Sheldrick, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

Figures

Fig. 1. A view of the structure of (I), showing the atomic numbering scheme. All H atoms have been omitted for clarity, and displacement ellipsoids are drawn at the 50% probability level for non-H atoms.

(Tetrahydrofuran)potassium Mer-[tris(carbazolyl)-trans-dichloro- (tetrahydrofurano)zirconate].

Crystal data

[K(C4H8O)][ZrCl2(C12H8N)3(C4H8O)]	Dx = 1.457 Mg m^−3
Mr = 844.01	Melting point: 470 - 472 K K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 7774 reflections
a = 14.158 (3) Å	θ = 2.3–28.3°
b = 15.486 (3) Å	µ = 0.58 mm^−1
c = 17.548 (3) Å	T = 173 K
V = 3847.4 (13) Å^3	Leaf-like, yellow
Z = 4	0.40 × 0.35 × 0.25 mm
F(000) = 1736

Data collection

Bruker AXS CCD diffractometer	9248 independent reflections
Radiation source: fine-focus sealed tube	8608 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.029
Detector resolution: not measured pixels mm^-1	θmax = 28.3°, θmin = 1.2°
ϕ and ω scans	h = −18→18
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −19→19
Tmin = 0.882, Tmax = 0.890	l = −23→23
41736 measured reflections

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)] = 0.028	H-atom parameters constrained
wR(F^2) = 0.078	w = 1/[σ^2(Fo^2) + (0.0454P)^2 + 1.0517P] where P = (Fo^2 + 2Fc^2)/3
S = 1.07	(Δ/σ)max = 0.005
9248 reflections	Δρmax = 0.75 e Å^−3
479 parameters	Δρmin = −0.34 e Å^−3
0 restraints	Absolute structure: Flack (1983), 5169 Friedel Pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.04 (2)

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	0.12967 (15)	0.00842 (14)	0.23524 (12)	0.0264 (4)
C2	0.05460 (17)	0.05603 (16)	0.20514 (14)	0.0335 (5)
H2	0.0620	0.1155	0.1931	0.040*
C3	−0.03056 (18)	0.01476 (18)	0.19328 (16)	0.0405 (6)
H3	−0.0819	0.0466	0.1726	0.049*
C4	−0.0432 (2)	−0.07187 (19)	0.21070 (16)	0.0420 (6)
H4	−0.1028	−0.0984	0.2022	0.050*
C5	0.03004 (17)	−0.11949 (15)	0.24020 (15)	0.0354 (5)
H5	0.0217	−0.1788	0.2521	0.043*
C6	0.11677 (15)	−0.07930 (14)	0.25231 (14)	0.0288 (4)
C7	0.20684 (17)	−0.11061 (14)	0.27881 (12)	0.0270 (4)
C8	0.23781 (19)	−0.19188 (15)	0.30363 (14)	0.0348 (5)
H8	0.1954	−0.2393	0.3063	0.042*
C9	0.3311 (2)	−0.20133 (16)	0.32411 (15)	0.0363 (6)
H9	0.3535	−0.2561	0.3404	0.044*
C10	0.39277 (18)	−0.13185 (16)	0.32123 (14)	0.0329 (5)
H10	0.4567	−0.1400	0.3361	0.039*
C11	0.36347 (17)	−0.05068 (14)	0.29721 (12)	0.0268 (4)
H11	0.4065	−0.0037	0.2957	0.032*
C12	0.26943 (16)	−0.03960 (13)	0.27531 (11)	0.0246 (4)
C13	0.31635 (16)	0.12666 (14)	0.42071 (12)	0.0256 (4)
C14	0.22817 (18)	0.08823 (14)	0.43309 (13)	0.0299 (5)
H14	0.1867	0.0759	0.3920	0.036*
C15	0.20389 (19)	0.06901 (16)	0.50736 (14)	0.0363 (5)
H15	0.1446	0.0424	0.5169	0.044*
C16	0.2625 (2)	0.08700 (18)	0.56853 (14)	0.0403 (6)
H16	0.2418	0.0750	0.6189	0.048*
C17	0.3510 (2)	0.12230 (17)	0.55669 (14)	0.0375 (6)
H17	0.3921	0.1336	0.5983	0.045*
C18	0.37826 (17)	0.14095 (14)	0.48222 (13)	0.0280 (5)
C19	0.46349 (16)	0.17499 (15)	0.45045 (12)	0.0281 (4)
C20	0.55034 (19)	0.19756 (16)	0.48255 (15)	0.0349 (5)
H20	0.5604	0.1920	0.5358	0.042*
C21	0.62083 (18)	0.22789 (16)	0.43611 (15)	0.0354 (5)
H21	0.6804	0.2428	0.4573	0.042*
C22	0.60558 (18)	0.23691 (15)	0.35806 (15)	0.0341 (5)
H22	0.6551	0.2584	0.3269	0.041*
C23	0.51942 (16)	0.21515 (14)	0.32450 (14)	0.0298 (5)
H23	0.5096	0.2220	0.2713	0.036*
C24	0.44857 (16)	0.18315 (13)	0.37126 (12)	0.0251 (4)
C25	0.31980 (16)	0.36832 (14)	0.28176 (13)	0.0263 (4)
C26	0.29414 (17)	0.36244 (15)	0.35839 (13)	0.0307 (5)
H26	0.2833	0.3079	0.3815	0.037*
C27	0.28471 (19)	0.43856 (16)	0.40022 (14)	0.0367 (5)
H27	0.2658	0.4356	0.4521	0.044*
C28	0.3026 (2)	0.51909 (16)	0.36729 (16)	0.0413 (6)
H28	0.2961	0.5699	0.3971	0.050*
C29	0.3295 (2)	0.52570 (15)	0.29223 (16)	0.0386 (6)
H29	0.3416	0.5806	0.2701	0.046*
C30	0.33900 (15)	0.45019 (13)	0.24883 (15)	0.0309 (4)
C31	0.36193 (17)	0.43464 (14)	0.17045 (14)	0.0302 (5)
C32	0.38629 (19)	0.48884 (16)	0.10983 (16)	0.0389 (6)
H32	0.3922	0.5493	0.1175	0.047*
C33	0.4015 (2)	0.45364 (18)	0.03939 (17)	0.0431 (6)
H33	0.4170	0.4900	−0.0024	0.052*
C34	0.3944 (2)	0.36484 (18)	0.02846 (15)	0.0392 (6)
H34	0.4048	0.3417	−0.0210	0.047*
C35	0.37270 (17)	0.30946 (16)	0.08771 (14)	0.0321 (5)
H35	0.3696	0.2489	0.0796	0.039*
C36	0.35542 (15)	0.34444 (14)	0.15981 (12)	0.0263 (4)
C37	0.2142 (2)	0.12155 (18)	0.07166 (14)	0.0435 (6)
H37A	0.2069	0.0626	0.0927	0.052*
H37B	0.2755	0.1252	0.0447	0.052*
C38	0.1347 (3)	0.1425 (2)	0.0190 (2)	0.0669 (10)
H38A	0.0751	0.1150	0.0358	0.080*
H38B	0.1490	0.1245	−0.0339	0.080*
C39	0.1301 (3)	0.2408 (2)	0.0262 (2)	0.0656 (10)
H39A	0.1800	0.2688	−0.0047	0.079*
H39B	0.0677	0.2630	0.0100	0.079*
C40	0.1461 (2)	0.25633 (18)	0.11051 (16)	0.0416 (6)
H40A	0.1762	0.3131	0.1195	0.050*
H40B	0.0860	0.2536	0.1392	0.050*
C41	0.4306 (4)	0.3720 (3)	0.5683 (3)	0.0917 (15)
H41A	0.4831	0.3467	0.5981	0.110*
H41B	0.4022	0.3258	0.5366	0.110*
C42	0.3598 (4)	0.4082 (3)	0.6193 (3)	0.0933 (14)
H42A	0.3742	0.3947	0.6732	0.112*
H42B	0.2958	0.3869	0.6068	0.112*
C43	0.3695 (4)	0.5075 (3)	0.6027 (3)	0.0981 (17)
H43A	0.3156	0.5283	0.5718	0.118*
H43B	0.3716	0.5407	0.6509	0.118*
C44	0.4581 (3)	0.5173 (3)	0.5608 (3)	0.0942 (16)
H44A	0.4555	0.5677	0.5261	0.113*
H44B	0.5121	0.5243	0.5960	0.113*
Cl1	0.13951 (4)	0.22028 (4)	0.30242 (3)	0.03044 (12)
Cl2	0.41799 (4)	0.10935 (4)	0.16801 (3)	0.03081 (12)
K1	0.50845 (4)	0.41900 (4)	0.37186 (4)	0.04415 (15)
N1	0.22338 (12)	0.03510 (10)	0.24940 (10)	0.0244 (3)
N2	0.35692 (13)	0.15473 (11)	0.35110 (10)	0.0237 (3)
N3	0.33002 (13)	0.30200 (12)	0.22761 (10)	0.0248 (4)
O1	0.20921 (12)	0.18554 (9)	0.13205 (9)	0.0300 (3)
O2	0.46524 (17)	0.44120 (19)	0.52020 (15)	0.0667 (7)
Zr1	0.283872 (13)	0.166257 (11)	0.244985 (10)	0.02106 (5)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0240 (10)	0.0298 (10)	0.0255 (11)	−0.0053 (8)	0.0003 (8)	−0.0021 (8)
C2	0.0284 (12)	0.0330 (12)	0.0391 (13)	−0.0047 (10)	−0.0029 (10)	0.0010 (10)
C3	0.0277 (12)	0.0472 (15)	0.0466 (15)	−0.0051 (11)	−0.0072 (11)	0.0000 (12)
C4	0.0294 (13)	0.0502 (15)	0.0464 (15)	−0.0165 (12)	−0.0009 (11)	−0.0040 (12)
C5	0.0331 (12)	0.0334 (11)	0.0397 (13)	−0.0117 (9)	0.0044 (11)	−0.0023 (10)
C6	0.0290 (10)	0.0316 (10)	0.0257 (10)	−0.0053 (8)	0.0033 (10)	−0.0020 (10)
C7	0.0311 (12)	0.0249 (10)	0.0249 (9)	−0.0038 (9)	0.0046 (9)	−0.0007 (8)
C8	0.0439 (15)	0.0246 (10)	0.0359 (12)	−0.0045 (9)	0.0052 (10)	0.0007 (9)
C9	0.0469 (15)	0.0263 (11)	0.0359 (13)	0.0046 (10)	0.0013 (11)	0.0041 (10)
C10	0.0335 (12)	0.0332 (12)	0.0319 (12)	0.0061 (10)	−0.0014 (10)	−0.0012 (9)
C11	0.0283 (11)	0.0255 (10)	0.0265 (10)	−0.0002 (9)	−0.0001 (9)	−0.0012 (8)
C12	0.0306 (12)	0.0215 (9)	0.0216 (9)	−0.0009 (8)	0.0017 (8)	−0.0014 (7)
C13	0.0298 (11)	0.0218 (10)	0.0254 (10)	0.0037 (8)	0.0027 (8)	0.0002 (8)
C14	0.0314 (12)	0.0272 (11)	0.0311 (11)	0.0011 (9)	0.0018 (9)	0.0006 (8)
C15	0.0342 (13)	0.0378 (13)	0.0370 (12)	0.0033 (11)	0.0082 (10)	0.0042 (10)
C16	0.0502 (16)	0.0453 (14)	0.0253 (11)	0.0108 (12)	0.0084 (10)	0.0054 (10)
C17	0.0462 (15)	0.0409 (13)	0.0255 (11)	0.0100 (12)	−0.0025 (10)	0.0011 (10)
C18	0.0329 (12)	0.0254 (10)	0.0257 (10)	0.0062 (9)	−0.0011 (9)	−0.0019 (8)
C19	0.0323 (12)	0.0233 (10)	0.0288 (10)	0.0036 (9)	−0.0041 (8)	−0.0033 (8)
C20	0.0381 (14)	0.0329 (12)	0.0338 (12)	0.0052 (10)	−0.0105 (10)	−0.0065 (9)
C21	0.0309 (12)	0.0281 (11)	0.0471 (14)	−0.0001 (9)	−0.0123 (10)	−0.0053 (10)
C22	0.0291 (12)	0.0279 (11)	0.0454 (14)	−0.0041 (9)	−0.0038 (10)	0.0013 (10)
C23	0.0304 (12)	0.0248 (10)	0.0342 (11)	−0.0043 (9)	−0.0028 (9)	0.0004 (9)
C24	0.0261 (11)	0.0195 (10)	0.0299 (10)	0.0009 (8)	−0.0039 (8)	−0.0005 (8)
C25	0.0235 (10)	0.0217 (9)	0.0336 (11)	−0.0007 (8)	−0.0062 (8)	−0.0037 (8)
C26	0.0289 (12)	0.0293 (10)	0.0340 (11)	−0.0006 (9)	−0.0047 (10)	−0.0040 (8)
C27	0.0343 (12)	0.0414 (13)	0.0343 (12)	0.0030 (11)	−0.0037 (11)	−0.0098 (10)
C28	0.0420 (15)	0.0313 (12)	0.0506 (15)	0.0045 (11)	−0.0056 (12)	−0.0177 (11)
C29	0.0413 (14)	0.0208 (11)	0.0535 (16)	0.0000 (10)	−0.0063 (12)	−0.0052 (10)
C30	0.0271 (10)	0.0244 (9)	0.0413 (12)	−0.0011 (8)	−0.0054 (11)	0.0008 (10)
C31	0.0268 (11)	0.0236 (10)	0.0403 (12)	0.0013 (9)	−0.0032 (10)	0.0032 (9)
C32	0.0381 (14)	0.0258 (11)	0.0529 (16)	−0.0036 (10)	0.0020 (12)	0.0116 (11)
C33	0.0426 (15)	0.0405 (14)	0.0462 (15)	−0.0040 (12)	0.0041 (12)	0.0171 (12)
C34	0.0395 (14)	0.0459 (14)	0.0324 (12)	−0.0032 (11)	0.0054 (10)	0.0049 (11)
C35	0.0316 (12)	0.0321 (12)	0.0326 (12)	−0.0050 (9)	0.0016 (10)	0.0007 (9)
C36	0.0220 (10)	0.0251 (10)	0.0316 (11)	−0.0029 (8)	−0.0014 (8)	0.0034 (9)
C37	0.0556 (17)	0.0456 (15)	0.0294 (11)	−0.0098 (14)	−0.0079 (13)	−0.0059 (10)
C38	0.080 (3)	0.069 (2)	0.0518 (19)	−0.0086 (19)	−0.0303 (18)	0.0003 (16)
C39	0.072 (2)	0.071 (2)	0.0535 (19)	−0.0071 (19)	−0.0291 (18)	0.0200 (17)
C40	0.0368 (14)	0.0394 (13)	0.0485 (15)	0.0031 (11)	−0.0119 (12)	0.0123 (11)
C41	0.124 (4)	0.077 (3)	0.075 (3)	0.054 (3)	−0.003 (3)	−0.001 (2)
C42	0.095 (3)	0.106 (4)	0.079 (3)	−0.018 (3)	0.000 (3)	−0.008 (3)
C43	0.087 (3)	0.100 (4)	0.107 (4)	0.026 (3)	−0.018 (3)	−0.052 (3)
C44	0.064 (3)	0.105 (4)	0.114 (4)	−0.015 (3)	0.000 (3)	−0.045 (3)
Cl1	0.0250 (3)	0.0285 (3)	0.0378 (3)	0.0036 (2)	0.0015 (2)	−0.0010 (2)
Cl2	0.0300 (3)	0.0300 (3)	0.0324 (3)	0.0040 (2)	0.0045 (2)	−0.0005 (2)
K1	0.0364 (3)	0.0373 (3)	0.0588 (4)	−0.0032 (2)	−0.0063 (3)	−0.0051 (3)
N1	0.0227 (8)	0.0231 (7)	0.0274 (8)	−0.0021 (6)	−0.0034 (9)	−0.0010 (7)
N2	0.0248 (9)	0.0216 (8)	0.0247 (8)	−0.0005 (7)	−0.0006 (7)	0.0004 (7)
N3	0.0255 (9)	0.0226 (8)	0.0263 (9)	−0.0013 (7)	−0.0014 (7)	0.0001 (7)
O1	0.0307 (8)	0.0247 (7)	0.0346 (8)	0.0002 (7)	−0.0053 (7)	0.0010 (6)
O2	0.0488 (14)	0.0867 (18)	0.0646 (15)	0.0081 (13)	−0.0056 (11)	−0.0115 (14)
Zr1	0.02106 (9)	0.01881 (8)	0.02332 (9)	−0.00083 (7)	−0.00184 (8)	0.00011 (7)

Geometric parameters (Å, º)

C1—C2	1.397 (3)	C27—K1	3.221 (3)
C1—C6	1.403 (3)	C27—H27	0.9500
C1—N1	1.412 (3)	C28—C29	1.375 (4)
C2—C3	1.380 (3)	C28—K1	3.302 (3)
C2—H2	0.9500	C28—H28	0.9500
C3—C4	1.388 (4)	C29—C30	1.402 (3)
C3—H3	0.9500	C29—K1	3.331 (3)
C4—C5	1.374 (4)	C29—H29	0.9500
C4—H4	0.9500	C30—C31	1.434 (4)
C5—C6	1.393 (3)	C30—K1	3.263 (2)
C5—H5	0.9500	C31—C32	1.398 (3)
C6—C7	1.441 (3)	C31—C36	1.412 (3)
C7—C8	1.402 (3)	C32—C33	1.368 (4)
C7—C12	1.414 (3)	C32—H32	0.9500
C8—C9	1.377 (4)	C33—C34	1.392 (4)
C8—H8	0.9500	C33—H33	0.9500
C9—C10	1.387 (4)	C34—C35	1.382 (3)
C9—H9	0.9500	C34—H34	0.9500
C10—C11	1.389 (3)	C35—C36	1.398 (3)
C10—H10	0.9500	C35—H35	0.9500
C11—C12	1.396 (3)	C36—N3	1.406 (3)
C11—K1^i	3.509 (2)	C37—O1	1.453 (3)
C11—H11	0.9500	C37—C38	1.491 (4)
C12—N1	1.404 (3)	C37—H37A	0.9900
C13—C14	1.400 (3)	C37—H37B	0.9900
C13—C18	1.408 (3)	C38—C39	1.530 (5)
C13—N2	1.418 (3)	C38—H38A	0.9900
C14—C15	1.380 (3)	C38—H38B	0.9900
C14—H14	0.9500	C39—C40	1.515 (4)
C15—C16	1.385 (4)	C39—H39A	0.9900
C15—K1^ii	3.490 (3)	C39—H39B	0.9900
C15—H15	0.9500	C40—O1	1.464 (3)
C16—C17	1.382 (4)	C40—H40A	0.9900
C16—H16	0.9500	C40—H40B	0.9900
C17—C18	1.393 (3)	C41—O2	1.450 (6)
C17—H17	0.9500	C41—C42	1.456 (7)
C18—C19	1.430 (3)	C41—H41A	0.9900
C19—C20	1.397 (3)	C41—H41B	0.9900
C19—C24	1.411 (3)	C42—C43	1.571 (7)
C20—C21	1.372 (4)	C42—H42A	0.9900
C20—H20	0.9500	C42—H42B	0.9900
C21—C22	1.394 (4)	C43—C44	1.462 (7)
C21—H21	0.9500	C43—H43A	0.9900
C22—C23	1.396 (3)	C43—H43B	0.9900
C22—K1	3.147 (3)	C44—O2	1.380 (5)
C22—H22	0.9500	C44—H44A	0.9900
C23—C24	1.387 (3)	C44—H44B	0.9900
C23—K1	3.268 (2)	Cl1—Zr1	2.4276 (7)
C23—H23	0.9500	Cl2—Zr1	2.4914 (6)
C24—N2	1.415 (3)	Cl2—K1^i	3.2036 (9)
C25—C26	1.396 (3)	K1—O2	2.696 (3)
C25—N3	1.407 (3)	K1—Cl2^iii	3.2036 (9)
C25—C30	1.420 (3)	K1—C15^iv	3.490 (3)
C25—K1	3.202 (2)	K1—C11^iii	3.509 (2)
C26—C27	1.395 (3)	N1—Zr1	2.2056 (16)
C26—K1	3.167 (3)	N2—Zr1	2.1374 (18)
C26—H26	0.9500	N3—Zr1	2.2224 (18)
C27—C28	1.397 (4)	O1—Zr1	2.2659 (16)
C2—C1—C6	119.5 (2)	C38—C37—H37B	110.6
C2—C1—N1	128.8 (2)	H37A—C37—H37B	108.8
C6—C1—N1	111.60 (19)	C37—C38—C39	101.4 (3)
C3—C2—C1	118.5 (2)	C37—C38—H38A	111.5
C3—C2—H2	120.7	C39—C38—H38A	111.5
C1—C2—H2	120.7	C37—C38—H38B	111.5
C2—C3—C4	121.8 (3)	C39—C38—H38B	111.5
C2—C3—H3	119.1	H38A—C38—H38B	109.3
C4—C3—H3	119.1	C40—C39—C38	103.4 (3)
C5—C4—C3	120.3 (2)	C40—C39—H39A	111.1
C5—C4—H4	119.9	C38—C39—H39A	111.1
C3—C4—H4	119.9	C40—C39—H39B	111.1
C4—C5—C6	118.9 (2)	C38—C39—H39B	111.1
C4—C5—H5	120.6	H39A—C39—H39B	109.0
C6—C5—H5	120.6	O1—C40—C39	103.0 (2)
C5—C6—C1	121.0 (2)	O1—C40—H40A	111.2
C5—C6—C7	132.8 (2)	C39—C40—H40A	111.2
C1—C6—C7	106.23 (18)	O1—C40—H40B	111.2
C8—C7—C12	121.0 (2)	C39—C40—H40B	111.2
C8—C7—C6	132.8 (2)	H40A—C40—H40B	109.1
C12—C7—C6	106.19 (19)	O2—C41—C42	107.8 (3)
C9—C8—C7	118.5 (2)	O2—C41—H41A	110.1
C9—C8—H8	120.8	C42—C41—H41A	110.1
C7—C8—H8	120.8	O2—C41—H41B	110.1
C8—C9—C10	120.8 (2)	C42—C41—H41B	110.1
C8—C9—H9	119.6	H41A—C41—H41B	108.5
C10—C9—H9	119.6	C41—C42—C43	101.7 (4)
C9—C10—C11	121.7 (2)	C41—C42—H42A	111.4
C9—C10—H10	119.2	C43—C42—H42A	111.4
C11—C10—H10	119.2	C41—C42—H42B	111.4
C10—C11—C12	118.6 (2)	C43—C42—H42B	111.4
C10—C11—K1^i	88.92 (14)	H42A—C42—H42B	109.3
C12—C11—K1^i	106.05 (13)	C44—C43—C42	105.6 (4)
C10—C11—H11	120.7	C44—C43—H43A	110.6
C12—C11—H11	120.7	C42—C43—H43A	110.6
K1^i—C11—H11	75.4	C44—C43—H43B	110.6
C11—C12—N1	129.30 (19)	C42—C43—H43B	110.6
C11—C12—C7	119.4 (2)	H43A—C43—H43B	108.7
N1—C12—C7	111.35 (19)	O2—C44—C43	103.6 (4)
C14—C13—C18	120.2 (2)	O2—C44—H44A	111.0
C14—C13—N2	128.7 (2)	C43—C44—H44A	111.0
C18—C13—N2	111.11 (19)	O2—C44—H44B	111.0
C15—C14—C13	117.4 (2)	C43—C44—H44B	111.0
C15—C14—H14	121.3	H44A—C44—H44B	109.0
C13—C14—H14	121.3	Zr1—Cl2—K1^i	133.76 (2)
C14—C15—C16	122.6 (2)	O2—K1—C22	106.72 (8)
C14—C15—K1^ii	139.40 (18)	O2—K1—C26	83.68 (7)
C16—C15—K1^ii	89.65 (16)	C22—K1—C26	99.50 (6)
C14—C15—H15	118.7	O2—K1—C25	108.59 (7)
C16—C15—H15	118.7	C22—K1—C25	96.14 (6)
C17—C16—C15	120.4 (2)	C26—K1—C25	25.32 (6)
C17—C16—H16	119.8	O2—K1—Cl2^iii	99.63 (6)
C15—C16—H16	119.8	C22—K1—Cl2^iii	131.73 (5)
C16—C17—C18	118.3 (2)	C26—K1—Cl2^iii	123.35 (5)
C16—C17—H17	120.8	C25—K1—Cl2^iii	112.89 (5)
C18—C17—H17	120.8	O2—K1—C27	67.40 (7)
C17—C18—C13	120.9 (2)	C22—K1—C27	121.74 (7)
C17—C18—C19	132.6 (2)	C26—K1—C27	25.21 (6)
C13—C18—C19	106.53 (19)	C25—K1—C27	43.85 (6)
C20—C19—C24	120.4 (2)	Cl2^iii—K1—C27	105.48 (5)
C20—C19—C18	132.7 (2)	O2—K1—C30	116.94 (7)
C24—C19—C18	106.9 (2)	C22—K1—C30	113.77 (6)
C21—C20—C19	119.1 (2)	C26—K1—C30	44.54 (6)
C21—C20—H20	120.4	C25—K1—C30	25.35 (6)
C19—C20—H20	120.4	Cl2^iii—K1—C30	87.61 (4)
C20—C21—C22	120.4 (2)	C27—K1—C30	50.60 (6)
C20—C21—H21	119.8	O2—K1—C23	112.30 (8)
C22—C21—H21	119.8	C22—K1—C23	25.05 (6)
C21—C22—C23	121.7 (2)	C26—K1—C23	76.08 (6)
C21—C22—K1	94.70 (16)	C25—K1—C23	71.17 (6)
C23—C22—K1	82.35 (14)	Cl2^iii—K1—C23	144.87 (5)
C21—C22—H22	119.1	C27—K1—C23	100.19 (6)
C23—C22—H22	119.1	C30—K1—C23	90.55 (6)
K1—C22—H22	93.0	O2—K1—C28	76.31 (7)
C24—C23—C22	117.9 (2)	C22—K1—C28	143.56 (7)
C24—C23—K1	99.22 (14)	C26—K1—C28	44.14 (6)
C22—C23—K1	72.60 (14)	C25—K1—C28	50.71 (6)
C24—C23—H23	121.0	Cl2^iii—K1—C28	81.36 (5)
C22—C23—H23	121.0	C27—K1—C28	24.70 (7)
K1—C23—H23	97.7	C30—K1—C28	42.74 (6)
C23—C24—C19	120.4 (2)	C23—K1—C28	119.29 (6)
C23—C24—N2	128.8 (2)	O2—K1—C29	99.74 (8)
C19—C24—N2	110.8 (2)	C22—K1—C29	138.12 (7)
C26—C25—N3	129.0 (2)	C26—K1—C29	51.50 (6)
C26—C25—C30	120.0 (2)	C25—K1—C29	43.96 (6)
N3—C25—C30	110.9 (2)	Cl2^iii—K1—C29	72.50 (5)
C26—C25—K1	75.96 (13)	C27—K1—C29	43.15 (7)
N3—C25—K1	115.26 (14)	C30—K1—C29	24.52 (6)
C30—C25—K1	79.76 (13)	C23—K1—C29	114.11 (6)
C27—C26—C25	118.5 (2)	C28—K1—C29	23.92 (7)
C27—C26—K1	79.55 (15)	O2—K1—C15^iv	65.59 (7)
C25—C26—K1	78.73 (14)	C22—K1—C15^iv	75.40 (6)
C27—C26—H26	120.8	C26—K1—C15^iv	145.04 (6)
C25—C26—H26	120.8	C25—K1—C15^iv	166.98 (6)
K1—C26—H26	111.6	Cl2^iii—K1—C15^iv	79.98 (4)
C26—C27—C28	121.3 (2)	C27—K1—C15^iv	132.91 (7)
C26—C27—K1	75.23 (15)	C30—K1—C15^iv	167.59 (6)
C28—C27—K1	80.90 (16)	C23—K1—C15^iv	99.68 (6)
C26—C27—H27	119.4	C28—K1—C15^iv	133.59 (7)
C28—C27—H27	119.4	C29—K1—C15^iv	146.21 (6)
K1—C27—H27	114.9	O2—K1—C11^iii	156.44 (7)
C29—C28—C27	120.9 (2)	C22—K1—C11^iii	80.15 (6)
C29—C28—K1	79.24 (16)	C26—K1—C11^iii	117.98 (6)
C27—C28—K1	74.40 (16)	C25—K1—C11^iii	92.66 (6)
C29—C28—H28	119.6	Cl2^iii—K1—C11^iii	61.59 (4)
C27—C28—H28	119.6	C27—K1—C11^iii	128.79 (6)
K1—C28—H28	117.5	C30—K1—C11^iii	78.51 (6)
C28—C29—C30	119.0 (2)	C23—K1—C11^iii	83.66 (6)
C28—C29—K1	76.83 (16)	C28—K1—C11^iii	111.89 (7)
C30—C29—K1	75.02 (14)	C29—K1—C11^iii	88.39 (7)
C28—C29—H29	120.5	C15^iv—K1—C11^iii	95.54 (6)
C30—C29—H29	120.5	C12—N1—C1	104.62 (16)
K1—C29—H29	118.6	C12—N1—Zr1	126.16 (13)
C29—C30—C25	120.4 (2)	C1—N1—Zr1	128.92 (14)
C29—C30—C31	133.1 (2)	C24—N2—C13	104.55 (17)
C25—C30—C31	106.5 (2)	C24—N2—Zr1	129.45 (14)
C29—C30—K1	80.47 (15)	C13—N2—Zr1	125.46 (14)
C25—C30—K1	74.90 (13)	C25—N3—C36	104.88 (18)
C31—C30—K1	116.32 (15)	C25—N3—Zr1	124.58 (15)
C32—C31—C36	120.6 (2)	C36—N3—Zr1	129.31 (14)
C32—C31—C30	133.2 (2)	C37—O1—C40	110.63 (19)
C36—C31—C30	106.16 (19)	C37—O1—Zr1	121.70 (15)
C33—C32—C31	119.1 (2)	C40—O1—Zr1	127.54 (14)
C33—C32—H32	120.4	C44—O2—C41	107.8 (3)
C31—C32—H32	120.4	C44—O2—K1	128.6 (3)
C32—C33—C34	120.4 (2)	C41—O2—K1	123.0 (2)
C32—C33—H33	119.8	N2—Zr1—N1	94.61 (7)
C34—C33—H33	119.8	N2—Zr1—N3	93.23 (7)
C35—C34—C33	121.7 (3)	N1—Zr1—N3	171.90 (7)
C35—C34—H34	119.2	N2—Zr1—O1	177.06 (6)
C33—C34—H34	119.2	N1—Zr1—O1	88.34 (6)
C34—C35—C36	118.6 (2)	N3—Zr1—O1	83.83 (6)
C34—C35—H35	120.7	N2—Zr1—Cl1	94.27 (5)
C36—C35—H35	120.7	N1—Zr1—Cl1	88.62 (5)
C35—C36—N3	129.0 (2)	N3—Zr1—Cl1	88.77 (5)
C35—C36—C31	119.4 (2)	O1—Zr1—Cl1	85.69 (5)
N3—C36—C31	111.5 (2)	N2—Zr1—Cl2	94.24 (5)
O1—C37—C38	105.5 (3)	N1—Zr1—Cl2	89.39 (5)
O1—C37—H37A	110.6	N3—Zr1—Cl2	92.07 (5)
C38—C37—H37A	110.6	O1—Zr1—Cl2	85.87 (5)
O1—C37—H37B	110.6	Cl1—Zr1—Cl2	171.38 (2)
C6—C1—C2—C3	0.2 (4)	C28—C27—K1—C30	−60.75 (14)
N1—C1—C2—C3	177.2 (2)	C26—C27—K1—C23	−17.13 (15)
C1—C2—C3—C4	0.3 (4)	C28—C27—K1—C23	−143.00 (15)
C2—C3—C4—C5	−0.4 (4)	C26—C27—K1—C28	125.9 (2)
C3—C4—C5—C6	0.1 (4)	C26—C27—K1—C29	97.40 (16)
C4—C5—C6—C1	0.3 (4)	C28—C27—K1—C29	−28.46 (14)
C4—C5—C6—C7	−177.1 (3)	C26—C27—K1—C15^iv	−130.73 (14)
C2—C1—C6—C5	−0.5 (3)	C28—C27—K1—C15^iv	103.41 (16)
N1—C1—C6—C5	−178.0 (2)	C26—C27—K1—C11^iii	72.90 (17)
C2—C1—C6—C7	177.6 (2)	C28—C27—K1—C11^iii	−52.97 (16)
N1—C1—C6—C7	0.0 (3)	C29—C30—K1—O2	48.94 (18)
C5—C6—C7—C8	−2.1 (5)	C25—C30—K1—O2	−76.25 (16)
C1—C6—C7—C8	−179.8 (2)	C31—C30—K1—O2	−177.47 (15)
C5—C6—C7—C12	177.0 (3)	C29—C30—K1—C22	174.14 (15)
C1—C6—C7—C12	−0.6 (2)	C25—C30—K1—C22	48.95 (16)
C12—C7—C8—C9	−0.5 (3)	C31—C30—K1—C22	−52.27 (17)
C6—C7—C8—C9	178.6 (2)	C29—C30—K1—C26	95.11 (17)
C7—C8—C9—C10	0.8 (4)	C25—C30—K1—C26	−30.08 (13)
C8—C9—C10—C11	−0.5 (4)	C31—C30—K1—C26	−131.30 (18)
C9—C10—C11—C12	−0.2 (4)	C29—C30—K1—C25	125.2 (2)
C9—C10—C11—K1^i	−108.0 (2)	C31—C30—K1—C25	−101.2 (2)
C10—C11—C12—N1	179.9 (2)	C29—C30—K1—Cl2^iii	−50.65 (15)
K1^i—C11—C12—N1	−82.4 (2)	C25—C30—K1—Cl2^iii	−175.85 (14)
C10—C11—C12—C7	0.6 (3)	C31—C30—K1—Cl2^iii	82.94 (15)
K1^i—C11—C12—C7	98.31 (19)	C29—C30—K1—C27	61.68 (16)
C8—C7—C12—C11	−0.2 (3)	C25—C30—K1—C27	−63.51 (14)
C6—C7—C12—C11	−179.49 (19)	C31—C30—K1—C27	−164.73 (18)
C8—C7—C12—N1	−179.65 (19)	C29—C30—K1—C23	164.45 (16)
C6—C7—C12—N1	1.1 (2)	C25—C30—K1—C23	39.25 (14)
C18—C13—C14—C15	2.7 (3)	C31—C30—K1—C23	−61.96 (16)
N2—C13—C14—C15	−178.1 (2)	C29—C30—K1—C28	29.18 (15)
C13—C14—C15—C16	0.6 (4)	C25—C30—K1—C28	−96.01 (17)
C13—C14—C15—K1^ii	138.0 (2)	C31—C30—K1—C28	162.8 (2)
C14—C15—C16—C17	−2.8 (4)	C25—C30—K1—C29	−125.2 (2)
K1^ii—C15—C16—C17	−156.6 (2)	C31—C30—K1—C29	133.6 (2)
C15—C16—C17—C18	1.5 (4)	C29—C30—K1—C15^iv	−49.9 (4)
C16—C17—C18—C13	1.9 (4)	C25—C30—K1—C15^iv	−175.1 (3)
C16—C17—C18—C19	−178.3 (2)	C31—C30—K1—C15^iv	83.7 (3)
C14—C13—C18—C17	−4.0 (3)	C29—C30—K1—C11^iii	−112.13 (16)
N2—C13—C18—C17	176.7 (2)	C25—C30—K1—C11^iii	122.67 (14)
C14—C13—C18—C19	176.09 (19)	C31—C30—K1—C11^iii	21.46 (15)
N2—C13—C18—C19	−3.2 (2)	C24—C23—K1—O2	34.75 (16)
C17—C18—C19—C20	3.5 (5)	C22—C23—K1—O2	−81.77 (16)
C13—C18—C19—C20	−176.7 (2)	C24—C23—K1—C22	116.5 (2)
C17—C18—C19—C24	−177.6 (3)	C24—C23—K1—C26	−42.29 (14)
C13—C18—C19—C24	2.2 (2)	C22—C23—K1—C26	−158.81 (16)
C24—C19—C20—C21	0.1 (3)	C24—C23—K1—C25	−68.20 (14)
C18—C19—C20—C21	178.9 (2)	C22—C23—K1—C25	175.28 (16)
C19—C20—C21—C22	0.7 (4)	C24—C23—K1—Cl2^iii	−171.47 (11)
C20—C21—C22—C23	−0.5 (4)	C22—C23—K1—Cl2^iii	72.01 (17)
C20—C21—C22—K1	83.4 (2)	C24—C23—K1—C27	−34.86 (15)
C21—C22—C23—C24	−0.6 (4)	C22—C23—K1—C27	−151.38 (15)
K1—C22—C23—C24	−91.4 (2)	C24—C23—K1—C30	−84.83 (15)
C21—C22—C23—K1	90.8 (2)	C22—C23—K1—C30	158.65 (16)
C22—C23—C24—C19	1.3 (3)	C24—C23—K1—C28	−51.62 (16)
K1—C23—C24—C19	−73.8 (2)	C22—C23—K1—C28	−168.14 (15)
C22—C23—C24—N2	−178.3 (2)	C24—C23—K1—C29	−77.83 (16)
K1—C23—C24—N2	106.6 (2)	C22—C23—K1—C29	165.65 (15)
C20—C19—C24—C23	−1.2 (3)	C24—C23—K1—C15^iv	102.23 (15)
C18—C19—C24—C23	179.8 (2)	C22—C23—K1—C15^iv	−14.29 (16)
C20—C19—C24—N2	178.5 (2)	C24—C23—K1—C11^iii	−163.20 (15)
C18—C19—C24—N2	−0.5 (2)	C22—C23—K1—C11^iii	80.28 (15)
N3—C25—C26—C27	−177.2 (2)	C29—C28—K1—O2	168.13 (17)
C30—C25—C26—C27	2.3 (3)	C27—C28—K1—O2	−65.35 (15)
K1—C25—C26—C27	71.4 (2)	C29—C28—K1—C22	−92.16 (19)
N3—C25—C26—K1	111.3 (2)	C27—C28—K1—C22	34.4 (2)
C30—C25—C26—K1	−69.1 (2)	C29—C28—K1—C26	−96.80 (16)
C25—C26—C27—C28	−1.5 (4)	C27—C28—K1—C26	29.72 (13)
K1—C26—C27—C28	69.4 (2)	C29—C28—K1—C25	−63.31 (15)
C25—C26—C27—K1	−71.0 (2)	C27—C28—K1—C25	63.20 (14)
C26—C27—C28—C29	0.4 (4)	C29—C28—K1—Cl2^iii	65.94 (15)
K1—C27—C28—C29	66.9 (3)	C27—C28—K1—Cl2^iii	−167.55 (15)
C26—C27—C28—K1	−66.5 (2)	C29—C28—K1—C27	−126.5 (2)
C27—C28—C29—C30	−0.1 (4)	C29—C28—K1—C30	−29.93 (13)
K1—C28—C29—C30	64.3 (2)	C27—C28—K1—C30	96.58 (16)
C27—C28—C29—K1	−64.4 (2)	C29—C28—K1—C23	−83.74 (16)
C28—C29—C30—C25	0.8 (4)	C27—C28—K1—C23	42.78 (17)
K1—C29—C30—C25	66.1 (2)	C27—C28—K1—C29	126.5 (2)
C28—C29—C30—C31	177.4 (3)	C29—C28—K1—C15^iv	133.13 (14)
K1—C29—C30—C31	−117.3 (3)	C27—C28—K1—C15^iv	−100.36 (15)
C28—C29—C30—K1	−65.3 (2)	C29—C28—K1—C11^iii	11.37 (16)
C26—C25—C30—C29	−2.0 (3)	C27—C28—K1—C11^iii	137.88 (14)
N3—C25—C30—C29	177.6 (2)	C28—C29—K1—O2	−11.70 (16)
K1—C25—C30—C29	−69.1 (2)	C30—C29—K1—O2	−137.00 (16)
C26—C25—C30—C31	−179.4 (2)	C28—C29—K1—C22	117.26 (16)
N3—C25—C30—C31	0.2 (3)	C30—C29—K1—C22	−8.0 (2)
K1—C25—C30—C31	113.52 (16)	C28—C29—K1—C26	62.08 (15)
C26—C25—C30—K1	67.1 (2)	C30—C29—K1—C26	−63.22 (15)
N3—C25—C30—K1	−113.28 (17)	C28—C29—K1—C25	95.04 (17)
C29—C30—C31—C32	2.7 (5)	C30—C29—K1—C25	−30.26 (13)
C25—C30—C31—C32	179.6 (3)	C28—C29—K1—Cl2^iii	−108.81 (15)
K1—C30—C31—C32	−99.4 (3)	C30—C29—K1—Cl2^iii	125.89 (16)
C29—C30—C31—C36	−176.9 (3)	C28—C29—K1—C27	29.42 (14)
C25—C30—C31—C36	0.0 (3)	C30—C29—K1—C27	−95.89 (17)
K1—C30—C31—C36	81.0 (2)	C28—C29—K1—C30	125.3 (2)
C36—C31—C32—C33	1.6 (4)	C28—C29—K1—C23	108.22 (15)
C30—C31—C32—C33	−177.9 (3)	C30—C29—K1—C23	−17.08 (17)
C31—C32—C33—C34	−1.1 (4)	C30—C29—K1—C28	−125.3 (2)
C32—C33—C34—C35	−0.5 (4)	C28—C29—K1—C15^iv	−71.9 (2)
C33—C34—C35—C36	1.5 (4)	C30—C29—K1—C15^iv	162.82 (14)
C34—C35—C36—N3	178.2 (2)	C28—C29—K1—C11^iii	−169.45 (15)
C34—C35—C36—C31	−0.9 (4)	C30—C29—K1—C11^iii	65.24 (15)
C32—C31—C36—C35	−0.6 (4)	C11—C12—N1—C1	179.6 (2)
C30—C31—C36—C35	179.0 (2)	C7—C12—N1—C1	−1.1 (2)
C32—C31—C36—N3	−179.9 (2)	C11—C12—N1—Zr1	−6.3 (3)
C30—C31—C36—N3	−0.3 (3)	C7—C12—N1—Zr1	173.07 (14)
O1—C37—C38—C39	32.8 (4)	C2—C1—N1—C12	−176.6 (2)
C37—C38—C39—C40	−40.2 (4)	C6—C1—N1—C12	0.6 (2)
C38—C39—C40—O1	32.2 (3)	C2—C1—N1—Zr1	9.5 (3)
O2—C41—C42—C43	−7.9 (5)	C6—C1—N1—Zr1	−173.27 (15)
C41—C42—C43—C44	−14.1 (5)	C23—C24—N2—C13	178.3 (2)
C42—C43—C44—O2	31.7 (5)	C19—C24—N2—C13	−1.3 (2)
C21—C22—K1—O2	−14.38 (18)	C23—C24—N2—Zr1	−9.9 (3)
C23—C22—K1—O2	107.04 (15)	C19—C24—N2—Zr1	170.49 (14)
C21—C22—K1—C26	−100.58 (16)	C14—C13—N2—C24	−176.4 (2)
C23—C22—K1—C26	20.84 (16)	C18—C13—N2—C24	2.8 (2)
C21—C22—K1—C25	−125.91 (16)	C14—C13—N2—Zr1	11.3 (3)
C23—C22—K1—C25	−4.49 (16)	C18—C13—N2—Zr1	−169.45 (14)
C21—C22—K1—Cl2^iii	105.76 (16)	C26—C25—N3—C36	179.2 (2)
C23—C22—K1—Cl2^iii	−132.82 (13)	C30—C25—N3—C36	−0.4 (2)
C21—C22—K1—C27	−87.76 (17)	K1—C25—N3—C36	−88.71 (17)
C23—C22—K1—C27	33.67 (18)	C26—C25—N3—Zr1	10.8 (3)
C21—C22—K1—C30	−144.86 (15)	C30—C25—N3—Zr1	−168.74 (15)
C23—C22—K1—C30	−23.44 (17)	K1—C25—N3—Zr1	102.97 (15)
C21—C22—K1—C23	−121.4 (2)	C35—C36—N3—C25	−178.8 (2)
C21—C22—K1—C28	−103.85 (18)	C31—C36—N3—C25	0.5 (2)
C23—C22—K1—C28	17.6 (2)	C35—C36—N3—Zr1	−11.2 (3)
C21—C22—K1—C29	−141.22 (16)	C31—C36—N3—Zr1	168.01 (16)
C23—C22—K1—C29	−19.8 (2)	C38—C37—O1—C40	−13.5 (3)
C21—C22—K1—C15^iv	44.01 (16)	C38—C37—O1—Zr1	162.5 (2)
C23—C22—K1—C15^iv	165.44 (16)	C39—C40—O1—C37	−12.1 (3)
C21—C22—K1—C11^iii	142.44 (17)	C39—C40—O1—Zr1	172.23 (19)
C23—C22—K1—C11^iii	−96.14 (15)	C43—C44—O2—C41	−37.7 (5)
C27—C26—K1—O2	47.73 (15)	C43—C44—O2—K1	133.3 (4)
C25—C26—K1—O2	169.80 (14)	C42—C41—O2—C44	29.3 (5)
C27—C26—K1—C22	153.69 (15)	C42—C41—O2—K1	−142.4 (3)
C25—C26—K1—C22	−84.24 (14)	C22—K1—O2—C44	151.4 (3)
C27—C26—K1—C25	−122.1 (2)	C26—K1—O2—C44	−110.5 (3)
C27—C26—K1—Cl2^iii	−49.66 (16)	C25—K1—O2—C44	−106.0 (3)
C25—C26—K1—Cl2^iii	72.41 (14)	Cl2^iii—K1—O2—C44	12.3 (3)
C25—C26—K1—C27	122.1 (2)	C27—K1—O2—C44	−90.6 (3)
C27—C26—K1—C30	−91.95 (16)	C30—K1—O2—C44	−79.9 (3)
C25—C26—K1—C30	30.12 (12)	C23—K1—O2—C44	177.4 (3)
C27—C26—K1—C23	162.62 (16)	C28—K1—O2—C44	−66.3 (3)
C25—C26—K1—C23	−75.31 (13)	C29—K1—O2—C44	−61.4 (3)
C27—C26—K1—C28	−29.10 (14)	C15^iv—K1—O2—C44	86.6 (3)
C25—C26—K1—C28	92.97 (16)	C11^iii—K1—O2—C44	47.4 (4)
C27—C26—K1—C29	−60.07 (15)	C22—K1—O2—C41	−38.8 (3)
C25—C26—K1—C29	62.00 (14)	C26—K1—O2—C41	59.3 (3)
C27—C26—K1—C15^iv	75.62 (18)	C25—K1—O2—C41	63.9 (3)
C25—C26—K1—C15^iv	−162.31 (13)	Cl2^iii—K1—O2—C41	−177.9 (3)
C27—C26—K1—C11^iii	−122.48 (14)	C27—K1—O2—C41	79.3 (3)
C25—C26—K1—C11^iii	−0.41 (15)	C30—K1—O2—C41	89.9 (3)
C26—C25—K1—O2	−10.70 (15)	C23—K1—O2—C41	−12.8 (3)
N3—C25—K1—O2	−137.57 (16)	C28—K1—O2—C41	103.6 (3)
C30—C25—K1—O2	113.99 (15)	C29—K1—O2—C41	108.4 (3)
C26—C25—K1—C22	99.27 (14)	C15^iv—K1—O2—C41	−103.6 (3)
N3—C25—K1—C22	−27.60 (17)	C11^iii—K1—O2—C41	−142.8 (3)
C30—C25—K1—C22	−136.04 (14)	C24—N2—Zr1—N1	139.20 (17)
N3—C25—K1—C26	−126.9 (2)	C13—N2—Zr1—N1	−50.51 (17)
C30—C25—K1—C26	124.7 (2)	C24—N2—Zr1—N3	−42.84 (18)
C26—C25—K1—Cl2^iii	−120.19 (13)	C13—N2—Zr1—N3	127.45 (17)
N3—C25—K1—Cl2^iii	112.94 (15)	C24—N2—Zr1—Cl1	−131.85 (17)
C30—C25—K1—Cl2^iii	4.50 (15)	C13—N2—Zr1—Cl1	38.44 (16)
C26—C25—K1—C27	−31.40 (13)	C24—N2—Zr1—Cl2	49.48 (17)
N3—C25—K1—C27	−158.3 (2)	C13—N2—Zr1—Cl2	−140.24 (16)
C30—C25—K1—C27	93.29 (16)	C12—N1—Zr1—N2	−39.25 (17)
C26—C25—K1—C30	−124.7 (2)	C1—N1—Zr1—N2	133.44 (18)
N3—C25—K1—C30	108.4 (2)	C12—N1—Zr1—O1	140.84 (17)
C26—C25—K1—C23	97.26 (14)	C1—N1—Zr1—O1	−46.47 (18)
N3—C25—K1—C23	−29.61 (15)	C12—N1—Zr1—Cl1	−133.43 (16)
C30—C25—K1—C23	−138.05 (15)	C1—N1—Zr1—Cl1	39.26 (17)
C26—C25—K1—C28	−63.98 (14)	C12—N1—Zr1—Cl2	54.95 (16)
N3—C25—K1—C28	169.1 (2)	C1—N1—Zr1—Cl2	−132.36 (17)
C30—C25—K1—C28	60.71 (15)	C25—N3—Zr1—N2	−51.67 (17)
C26—C25—K1—C29	−95.44 (16)	C36—N3—Zr1—N2	142.97 (19)
N3—C25—K1—C29	137.7 (2)	C25—N3—Zr1—O1	128.34 (18)
C30—C25—K1—C29	29.25 (14)	C36—N3—Zr1—O1	−37.02 (18)
C26—C25—K1—C15^iv	50.6 (3)	C25—N3—Zr1—Cl1	42.54 (17)
N3—C25—K1—C15^iv	−76.3 (3)	C36—N3—Zr1—Cl1	−122.82 (18)
C30—C25—K1—C15^iv	175.3 (3)	C25—N3—Zr1—Cl2	−146.04 (17)
C26—C25—K1—C11^iii	179.64 (13)	C36—N3—Zr1—Cl2	48.60 (18)
N3—C25—K1—C11^iii	52.77 (16)	C37—O1—Zr1—N1	−48.06 (19)
C30—C25—K1—C11^iii	−55.67 (14)	C40—O1—Zr1—N1	127.22 (19)
C26—C27—K1—O2	−127.18 (17)	C37—O1—Zr1—N3	133.98 (19)
C28—C27—K1—O2	106.95 (16)	C40—O1—Zr1—N3	−50.74 (19)
C26—C27—K1—C22	−30.93 (17)	C37—O1—Zr1—Cl1	−136.80 (18)
C28—C27—K1—C22	−156.79 (14)	C40—O1—Zr1—Cl1	38.49 (18)
C28—C27—K1—C26	−125.9 (2)	C37—O1—Zr1—Cl2	41.44 (18)
C26—C27—K1—C25	31.54 (13)	C40—O1—Zr1—Cl2	−143.27 (19)
C28—C27—K1—C25	−94.33 (16)	K1^i—Cl2—Zr1—N2	82.41 (6)
C26—C27—K1—Cl2^iii	138.65 (14)	K1^i—Cl2—Zr1—N1	−12.16 (6)
C28—C27—K1—Cl2^iii	12.78 (15)	K1^i—Cl2—Zr1—N3	175.81 (6)
C26—C27—K1—C30	65.11 (14)	K1^i—Cl2—Zr1—O1	−100.54 (5)

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) x−1/2, −y+1/2, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) x+1/2, −y+1/2, −z+1.