Bis­[(1R,2R)-(−)-1,2-bis­(tri­methyl­silyl­amino)­cyclo­hexane(2−)-κ²N,N′]­zirconium(IV)

The title complex, [(1R,2R)-(–)-1,2-(NSiMe₃)₂-C₆H₁₀]₂Zr or [Zr(C₁₂H₂₈N₂Si₂)₂], can be viewed as a tetrahedron located on a non-crystallographic twofold axis, which passes through the Zr atom and between the two N atoms of each cyclo­hexane-based ligand. The amide N atoms form two almost perpendicular planes with the central Zr atom, with a dihedral angle of 87.23 (18)°.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.012 Å
• R factor = 0.047
• wR factor = 0.109
• Data-to-parameter ratio = 14.9

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           25.04
         From the CIF: _reflns_number_total               4626
         Count of symmetry unique reflns         3149
         Completeness (_total/calc)            146.90%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured      1477
         Fraction of Friedel pairs measured     0.469
         Are heavy atom types Z>Si present          yes
          WARNING: Large fraction of Friedel related reflns may
                   be needed to determine absolute structure

---

S1. Comment

Group 4 metal complexes containing bidentate bis(amide) or tetradentate bis(amidinate) ligands are promising systems for applications in catalysis because of their relationship to the well studied metallocene analogues Cp₂MX₂, bis(amide) (R₂N)₂MX₂ (Minhas et al., 1996), and bis(amidinate) [N(R)C(R')N(R)]₂MX₂ (Bambirra et al., 2001; Foley et al., 2000). An attractive goal in this area is to develop chiral metal complexes for exploitation in stereoselective catalysis (Hagadorn & Arnold, 1998). The (1R,2R)-DACH served as broad-range chiral reagents has been proved a useful building block (Larrow et al., 1994). Recently, we reported the chemistry of its lithium derivatives, including mono- and dilithium (1R,2R)-(-)-1,2-(NHSiMe₃)₂-C₆H₁₀, and grew single crystals suitable for X-ray diffraction analysis (Li et al., 2002). Using this approach for the preparation of transition-metal complexes, we now reported the syntheses and structures of zirconium bis(amide) tetra-dentate complex, (I).

The molecular structure of (I) is shown in Fig. 1. The two cyclohexyl groups adopt chair conformations. The molecule of (I) is located on a crstallographic twofold axis, which passes through the Zr atom and the center of the N2—N1 and N3—N4 bonds, and therefore has high symmetry (Fig. 2). The structure can be viewed as a tetrahedron, with the metal ion in the center bonded to two bidentate ligands.

All the amide N atoms are sp²-hybridized (for example, the sum of the angles around N1 is 358.5°). The geometry around Zr is distorted tetrahedral, with the four Zr—N bond distances in the range 2.058 (4)–2.077 (5) Å and similar to the literature values (Lee et al., 2000). The five-membered Zr—N—C—C—N ring adopts an envelope conformation. From Table 1, we note that the intraannular N—Zr—N' angles, N1—Zr1—N2 [86.8 (2)°] and N3—Zr1—N4 [86.72 (19)°], are significantly smaller than the ideal tetrahedral value due to chelation, while the other two N—Zr—N' angles between the two chelate rings, N1—Zr1—N3 [121.71 (19)°] and N2—Zr1—N4 [119.06 (18)°] are correspondingly larger. The N1—Zr1—N2 and N3—Zr1—N4 planes are almost vertical and the dihedral angle is 92.8°. In addition, the two NSiMe₃ groups related by the crystallographically imposed C₂ axis are symmetrically placed above and below the opposite N—Zr—N' plane, similar to the complex {(±)-trans-1,2-(NSiMe₃)₂-C₆H₁₀}TiI₂ (Tsuie et al., 1997).

S2. Experimental

Li₂[(1R,2R)-(-)-1,2-(NSiMe₃)₂-C₆H₁₀] can be translated to its sodium salt easily in hexane. When two equivalents of NaBu^t was added to the clear solution of dilithium salt at room temperature, a white precipitate formed immediately. The mixture was stirred overnight and filtered. The white precipitate which was isolated was dried in a vacuum to give Na₂[(1R,2R)-(-)-1,2-(NSiMe₃)₂-C₆H₁₀]. Treatment of Na₂[(1R,2R)-(-)-1,2-(NSiMe₃)₂-C₆H₁₀] with a half equivalent of ZrCl₄ in toluene at low temperature gave a yellow solution. After filtering, the reaction afforded a colorless crystalline product in high yield. Spectroscopic analysis, ¹H NMR (CDCl₃, δ, p.p.m.): 0.02 (s, 36H, SiMe3), 1.15 (m, 8H, CH), 1.59 (m, 8H, CH), 3.56 (m, 4H, CH); ¹³C NMR (CDCl₃, δ, p.p.m.): 2.42, 25.83, 36.26, 65.95.

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 0.98 Å and U_iso(H) = 1.5U_eq(C), but each group was allowed to rotate freely about its C—C bond. The position of the amine H atom was refined freely along with an isotropic displacement parameter. All other H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.95–1.00 Å and U_iso(H) = 1.2U_eq(C).

Computing details

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. View of the molecule of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented by small spheres of arbitrary radii.
	Fig. 2. A diagram of the molecule of (I), viewed along the crstallographic twofold axis, all H atoms have been omitted for clarity.
	Fig. 3. A packing diagram of the title complex.

bis[(1R,2R)-(-)-1,2-bis(trimethylsilylamino)cyclohexane-κ²N,N']zirconium

Crystal data

[Zr(C12H28N2Si2)2]	Dx = 1.125 Mg m^−3
Mr = 604.31	Mo Kα radiation, λ = 0.71073 Å
Trigonal, P31	Cell parameters from 956 reflections
a = 10.473 (5) Å	θ = 2.3–27.0°
c = 28.166 (18) Å	µ = 0.46 mm^−1
V = 2676 (2) Å^3	T = 298 K
Z = 3	Block, colorless
F(000) = 972	0.35 × 0.30 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer	4626 independent reflections
Radiation source: fine-focus sealed tube	4526 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.038
ω scans	θmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	h = −12→11
Tmin = 0.856, Tmax = 0.956	k = −12→12
11157 measured reflections	l = −33→20

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)] = 0.047	H atoms treated by a mixture of independent and constrained refinement
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0337P)^2 + 2.5967P] where P = (Fo^2 + 2Fc^2)/3
S = 1.28	(Δ/σ)max = 0.003
4626 reflections	Δρmax = 0.48 e Å^−3
310 parameters	Δρmin = −1.04 e Å^−3
1 restraint	Absolute structure: Flack (1983), 0000 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.03 (6)

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	0.27699 (5)	0.22031 (6)	0.23036 (2)	0.04014 (14)
Si1	0.3511 (2)	0.4663 (2)	0.14258 (8)	0.0591 (5)
Si2	0.0084 (2)	−0.1279 (2)	0.25372 (8)	0.0604 (5)
Si3	0.2034 (2)	0.3955 (2)	0.31761 (8)	0.0642 (5)
Si4	0.5477 (2)	0.1437 (2)	0.20739 (7)	0.0529 (4)
N1	0.2373 (5)	0.2965 (5)	0.16764 (18)	0.0419 (11)
N2	0.0851 (5)	0.0247 (5)	0.21697 (19)	0.0499 (12)
N3	0.3166 (5)	0.3367 (6)	0.29350 (19)	0.0463 (12)
N4	0.4678 (5)	0.2158 (5)	0.24396 (17)	0.0407 (11)
C1	0.1160 (7)	0.1704 (6)	0.1428 (2)	0.0454 (14)
H1	0.1602	0.1233	0.1242	0.054*
C2	0.0296 (8)	0.2101 (8)	0.1083 (3)	0.0620 (18)
H2A	0.0971	0.2826	0.0859	0.074*
H2B	−0.0188	0.2540	0.1257	0.074*
C3	−0.0865 (8)	0.0746 (9)	0.0812 (3)	0.074 (2)
H3A	−0.1439	0.1029	0.0613	0.088*
H3B	−0.0376	0.0379	0.0607	0.088*
C4	−0.1880 (9)	−0.0458 (9)	0.1146 (3)	0.084 (3)
H4A	−0.2529	−0.1333	0.0964	0.101*
H4B	−0.2487	−0.0146	0.1314	0.101*
C5	−0.1031 (8)	−0.0839 (8)	0.1507 (3)	0.071 (2)
H5A	−0.1718	−0.1575	0.1727	0.085*
H5B	−0.0506	−0.1253	0.1344	0.085*
C6	0.0061 (6)	0.0528 (7)	0.1781 (2)	0.0501 (15)
H6	−0.0503	0.0939	0.1928	0.060*
C7	0.4256 (11)	0.4550 (11)	0.0833 (4)	0.101 (3)
H7A	0.4770	0.4010	0.0863	0.152*
H7B	0.4923	0.5527	0.0720	0.152*
H7C	0.3457	0.4056	0.0613	0.152*
C8	0.2634 (12)	0.5829 (9)	0.1356 (4)	0.101 (3)
H8A	0.1895	0.5420	0.1112	0.152*
H8B	0.3372	0.6813	0.1269	0.152*
H8C	0.2186	0.5854	0.1651	0.152*
C9	0.5089 (9)	0.5618 (9)	0.1851 (4)	0.093 (3)
H9A	0.4733	0.5771	0.2148	0.140*
H9B	0.5807	0.6552	0.1721	0.140*
H9C	0.5533	0.5020	0.1902	0.140*
C10	−0.1699 (9)	−0.1626 (11)	0.2808 (4)	0.094 (3)
H10A	−0.1545	−0.0758	0.2973	0.142*
H10B	−0.2046	−0.2433	0.3027	0.142*
H10C	−0.2419	−0.1864	0.2562	0.142*
C11	−0.0191 (13)	−0.3010 (10)	0.2233 (4)	0.118 (4)
H11A	−0.0725	−0.3153	0.1943	0.177*
H11B	−0.0740	−0.3842	0.2438	0.177*
H11C	0.0751	−0.2913	0.2165	0.177*
C12	0.1440 (9)	−0.0853 (10)	0.3022 (3)	0.077 (2)
H12A	0.2396	−0.0532	0.2888	0.115*
H12B	0.1145	−0.1721	0.3210	0.115*
H12C	0.1479	−0.0085	0.3219	0.115*
C13	0.4331 (6)	0.3223 (7)	0.3186 (2)	0.0448 (14)
H13	0.3847	0.2280	0.3356	0.054*
C14	0.5178 (8)	0.4452 (8)	0.3560 (3)	0.0645 (18)
H14A	0.5729	0.5398	0.3403	0.077*
H14B	0.4483	0.4501	0.3776	0.077*
C15	0.6230 (10)	0.4127 (9)	0.3838 (3)	0.076 (2)
H15A	0.6792	0.4926	0.4059	0.092*
H15B	0.5666	0.3230	0.4020	0.092*
C16	0.7270 (10)	0.3951 (11)	0.3514 (3)	0.089 (3)
H16A	0.7859	0.3656	0.3699	0.107*
H16B	0.7932	0.4893	0.3367	0.107*
C17	0.6456 (8)	0.2808 (9)	0.3127 (3)	0.0659 (19)
H17A	0.5878	0.1843	0.3271	0.079*
H17B	0.7166	0.2774	0.2914	0.079*
C18	0.5441 (6)	0.3184 (6)	0.2845 (2)	0.0441 (14)
H18	0.6046	0.4177	0.2715	0.053*
C19	0.1210 (12)	0.3026 (12)	0.3753 (3)	0.106 (3)
H19A	0.0340	0.2094	0.3693	0.159*
H19B	0.0955	0.3637	0.3937	0.159*
H19C	0.1912	0.2868	0.3924	0.159*
C20	0.2951 (12)	0.5980 (10)	0.3254 (4)	0.109 (3)
H20A	0.3817	0.6308	0.3446	0.163*
H20B	0.2286	0.6229	0.3408	0.163*
H20C	0.3225	0.6451	0.2950	0.163*
C21	0.0532 (10)	0.3464 (12)	0.2739 (4)	0.103 (3)
H21A	0.0940	0.3691	0.2424	0.155*
H21B	0.0048	0.4018	0.2805	0.155*
H21C	−0.0168	0.2429	0.2761	0.155*
C22	0.7322 (8)	0.2875 (10)	0.1855 (3)	0.077 (2)
H22A	0.7276	0.3729	0.1757	0.116*
H22B	0.7607	0.2495	0.1591	0.116*
H22C	0.8034	0.3143	0.2105	0.116*
C23	0.4228 (10)	0.0661 (11)	0.1551 (3)	0.087 (3)
H23A	0.3229	0.0070	0.1659	0.131*
H23B	0.4503	0.0062	0.1369	0.131*
H23C	0.4309	0.1452	0.1357	0.131*
C24	0.5645 (11)	−0.0086 (10)	0.2349 (4)	0.094 (3)
H24A	0.6541	0.0319	0.2530	0.140*
H24B	0.5664	−0.0715	0.2104	0.140*
H24C	0.4818	−0.0648	0.2554	0.140*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zr1	0.0392 (3)	0.0448 (3)	0.0367 (3)	0.0212 (3)	−0.0049 (3)	−0.0025 (3)
Si1	0.0565 (11)	0.0578 (11)	0.0561 (12)	0.0234 (9)	0.0005 (10)	0.0135 (10)
Si2	0.0561 (10)	0.0488 (10)	0.0645 (13)	0.0174 (8)	0.0017 (9)	0.0103 (9)
Si3	0.0790 (13)	0.0715 (13)	0.0574 (13)	0.0490 (11)	0.0055 (11)	−0.0091 (10)
Si4	0.0527 (10)	0.0657 (11)	0.0515 (11)	0.0380 (9)	−0.0026 (8)	−0.0057 (9)
N1	0.038 (2)	0.050 (3)	0.040 (3)	0.024 (2)	−0.005 (2)	0.000 (2)
N2	0.038 (3)	0.051 (3)	0.048 (3)	0.012 (2)	−0.002 (2)	0.000 (2)
N3	0.046 (3)	0.052 (3)	0.040 (3)	0.023 (2)	0.001 (2)	−0.006 (2)
N4	0.038 (2)	0.049 (3)	0.038 (3)	0.024 (2)	−0.007 (2)	−0.003 (2)
C1	0.053 (3)	0.053 (3)	0.035 (3)	0.030 (3)	−0.004 (3)	−0.005 (3)
C2	0.062 (4)	0.075 (4)	0.054 (4)	0.037 (4)	−0.009 (3)	0.002 (4)
C3	0.071 (5)	0.091 (6)	0.053 (5)	0.038 (4)	−0.024 (4)	−0.015 (4)
C4	0.070 (5)	0.088 (6)	0.074 (6)	0.024 (4)	−0.038 (4)	−0.020 (5)
C5	0.059 (4)	0.064 (4)	0.063 (5)	0.011 (3)	−0.009 (4)	0.000 (4)
C6	0.037 (3)	0.062 (4)	0.043 (4)	0.018 (3)	−0.016 (3)	−0.015 (3)
C7	0.098 (7)	0.120 (8)	0.088 (7)	0.057 (6)	0.040 (6)	0.037 (6)
C8	0.140 (8)	0.063 (5)	0.112 (8)	0.060 (6)	−0.013 (7)	0.012 (5)
C9	0.070 (5)	0.059 (5)	0.117 (8)	0.007 (4)	0.000 (5)	0.026 (5)
C10	0.061 (5)	0.111 (7)	0.090 (7)	0.027 (5)	0.013 (5)	0.035 (6)
C11	0.158 (10)	0.062 (5)	0.124 (10)	0.048 (6)	−0.007 (8)	−0.001 (6)
C12	0.064 (5)	0.091 (6)	0.075 (6)	0.038 (4)	0.016 (4)	0.033 (5)
C13	0.045 (3)	0.044 (3)	0.038 (3)	0.016 (3)	−0.008 (3)	−0.002 (3)
C14	0.076 (5)	0.061 (4)	0.046 (4)	0.027 (4)	−0.012 (4)	−0.017 (3)
C15	0.090 (6)	0.074 (5)	0.050 (5)	0.031 (4)	−0.029 (4)	−0.011 (4)
C16	0.081 (5)	0.115 (7)	0.070 (6)	0.049 (5)	−0.030 (5)	−0.007 (5)
C17	0.065 (4)	0.092 (5)	0.058 (5)	0.052 (4)	−0.017 (4)	−0.005 (4)
C18	0.042 (3)	0.047 (3)	0.039 (3)	0.019 (3)	−0.009 (3)	0.000 (3)
C19	0.130 (8)	0.129 (8)	0.073 (6)	0.075 (7)	0.042 (6)	0.009 (6)
C20	0.150 (9)	0.091 (6)	0.114 (9)	0.082 (7)	−0.020 (7)	−0.022 (6)
C21	0.096 (6)	0.142 (8)	0.111 (8)	0.089 (7)	−0.006 (6)	−0.035 (7)
C22	0.073 (5)	0.102 (6)	0.061 (5)	0.047 (4)	0.017 (4)	0.003 (4)
C23	0.096 (6)	0.122 (7)	0.062 (6)	0.068 (6)	−0.024 (5)	−0.040 (5)
C24	0.115 (7)	0.090 (6)	0.106 (8)	0.074 (6)	0.004 (6)	0.005 (6)

Geometric parameters (Å, º)

Zr1—N4	2.058 (4)	C9—H9A	0.9600
Zr1—N2	2.064 (5)	C9—H9B	0.9600
Zr1—N1	2.064 (5)	C9—H9C	0.9600
Zr1—N3	2.077 (5)	C10—H10A	0.9600
Si1—N1	1.721 (5)	C10—H10B	0.9600
Si1—C8	1.870 (8)	C10—H10C	0.9600
Si1—C7	1.870 (9)	C11—H11A	0.9600
Si1—C9	1.874 (9)	C11—H11B	0.9600
Si2—N2	1.728 (5)	C11—H11C	0.9600
Si2—C12	1.857 (9)	C12—H12A	0.9600
Si2—C10	1.877 (8)	C12—H12B	0.9600
Si2—C11	1.892 (10)	C12—H12C	0.9600
Si3—N3	1.726 (5)	C13—C18	1.524 (9)
Si3—C20	1.852 (9)	C13—C14	1.554 (8)
Si3—C21	1.857 (10)	C13—H13	0.9800
Si3—C19	1.868 (9)	C14—C15	1.522 (10)
Si4—N4	1.721 (5)	C14—H14A	0.9700
Si4—C24	1.859 (8)	C14—H14B	0.9700
Si4—C22	1.864 (8)	C15—C16	1.501 (12)
Si4—C23	1.864 (8)	C15—H15A	0.9700
N1—C1	1.473 (7)	C15—H15B	0.9700
N2—C6	1.488 (8)	C16—C17	1.524 (11)
N3—C13	1.481 (8)	C16—H16A	0.9700
N4—C18	1.497 (7)	C16—H16B	0.9700
C1—C2	1.521 (8)	C17—C18	1.527 (8)
C1—C6	1.553 (9)	C17—H17A	0.9700
C1—H1	0.9800	C17—H17B	0.9700
C2—C3	1.533 (10)	C18—H18	0.9800
C2—H2A	0.9700	C19—H19A	0.9600
C2—H2B	0.9700	C19—H19B	0.9600
C3—C4	1.505 (12)	C19—H19C	0.9600
C3—H3A	0.9700	C20—H20A	0.9600
C3—H3B	0.9700	C20—H20B	0.9600
C4—C5	1.530 (11)	C20—H20C	0.9600
C4—H4A	0.9700	C21—H21A	0.9600
C4—H4B	0.9700	C21—H21B	0.9600
C5—C6	1.522 (9)	C21—H21C	0.9600
C5—H5A	0.9700	C22—H22A	0.9600
C5—H5B	0.9700	C22—H22B	0.9600
C6—H6	0.9800	C22—H22C	0.9600
C7—H7A	0.9600	C23—H23A	0.9600
C7—H7B	0.9600	C23—H23B	0.9600
C7—H7C	0.9600	C23—H23C	0.9600
C8—H8A	0.9600	C24—H24A	0.9600
C8—H8B	0.9600	C24—H24B	0.9600
C8—H8C	0.9600	C24—H24C	0.9600
N4—Zr1—N2	119.06 (18)	Si1—C9—H9C	109.5
N4—Zr1—N1	123.59 (19)	H9A—C9—H9C	109.5
N2—Zr1—N1	86.8 (2)	H9B—C9—H9C	109.5
N4—Zr1—N3	86.72 (19)	Si2—C10—H10A	109.5
N2—Zr1—N3	123.3 (2)	Si2—C10—H10B	109.5
N1—Zr1—N3	121.71 (19)	H10A—C10—H10B	109.5
N1—Si1—C8	113.9 (4)	Si2—C10—H10C	109.5
N1—Si1—C7	113.3 (4)	H10A—C10—H10C	109.5
C8—Si1—C7	107.7 (5)	H10B—C10—H10C	109.5
N1—Si1—C9	105.1 (3)	Si2—C11—H11A	109.5
C8—Si1—C9	108.0 (5)	Si2—C11—H11B	109.5
C7—Si1—C9	108.7 (5)	H11A—C11—H11B	109.5
N2—Si2—C12	105.8 (3)	Si2—C11—H11C	109.5
N2—Si2—C10	112.3 (4)	H11A—C11—H11C	109.5
C12—Si2—C10	108.4 (4)	H11B—C11—H11C	109.5
N2—Si2—C11	113.1 (4)	Si2—C12—H12A	109.5
C12—Si2—C11	107.1 (5)	Si2—C12—H12B	109.5
C10—Si2—C11	109.8 (5)	H12A—C12—H12B	109.5
N3—Si3—C20	113.6 (4)	Si2—C12—H12C	109.5
N3—Si3—C21	106.1 (3)	H12A—C12—H12C	109.5
C20—Si3—C21	106.2 (5)	H12B—C12—H12C	109.5
N3—Si3—C19	112.1 (4)	N3—C13—C18	112.4 (5)
C20—Si3—C19	109.5 (5)	N3—C13—C14	113.5 (5)
C21—Si3—C19	109.0 (5)	C18—C13—C14	108.8 (5)
N4—Si4—C24	113.8 (4)	N3—C13—H13	107.3
N4—Si4—C22	112.2 (3)	C18—C13—H13	107.3
C24—Si4—C22	109.0 (4)	C14—C13—H13	107.3
N4—Si4—C23	105.9 (3)	C15—C14—C13	109.9 (6)
C24—Si4—C23	107.6 (5)	C15—C14—H14A	109.7
C22—Si4—C23	108.0 (4)	C13—C14—H14A	109.7
C1—N1—Si1	125.0 (4)	C15—C14—H14B	109.7
C1—N1—Zr1	108.0 (4)	C13—C14—H14B	109.7
Si1—N1—Zr1	125.5 (3)	H14A—C14—H14B	108.2
C6—N2—Si2	125.2 (4)	C16—C15—C14	111.5 (7)
C6—N2—Zr1	107.4 (4)	C16—C15—H15A	109.3
Si2—N2—Zr1	125.5 (3)	C14—C15—H15A	109.3
C13—N3—Si3	126.6 (4)	C16—C15—H15B	109.3
C13—N3—Zr1	106.4 (4)	C14—C15—H15B	109.3
Si3—N3—Zr1	125.1 (3)	H15A—C15—H15B	108.0
C18—N4—Si4	124.7 (4)	C15—C16—C17	112.1 (7)
C18—N4—Zr1	107.6 (3)	C15—C16—H16A	109.2
Si4—N4—Zr1	126.1 (3)	C17—C16—H16A	109.2
N1—C1—C2	115.0 (5)	C15—C16—H16B	109.2
N1—C1—C6	111.8 (5)	C17—C16—H16B	109.2
C2—C1—C6	108.6 (5)	H16A—C16—H16B	107.9
N1—C1—H1	107.0	C16—C17—C18	110.9 (6)
C2—C1—H1	107.0	C16—C17—H17A	109.5
C6—C1—H1	107.0	C18—C17—H17A	109.5
C1—C2—C3	111.7 (6)	C16—C17—H17B	109.5
C1—C2—H2A	109.3	C18—C17—H17B	109.5
C3—C2—H2A	109.3	H17A—C17—H17B	108.0
C1—C2—H2B	109.3	N4—C18—C13	111.1 (5)
C3—C2—H2B	109.3	N4—C18—C17	113.8 (5)
H2A—C2—H2B	107.9	C13—C18—C17	108.6 (5)
C4—C3—C2	111.4 (6)	N4—C18—H18	107.7
C4—C3—H3A	109.3	C13—C18—H18	107.7
C2—C3—H3A	109.3	C17—C18—H18	107.7
C4—C3—H3B	109.3	Si3—C19—H19A	109.5
C2—C3—H3B	109.3	Si3—C19—H19B	109.5
H3A—C3—H3B	108.0	H19A—C19—H19B	109.5
C3—C4—C5	112.0 (6)	Si3—C19—H19C	109.5
C3—C4—H4A	109.2	H19A—C19—H19C	109.5
C5—C4—H4A	109.2	H19B—C19—H19C	109.5
C3—C4—H4B	109.2	Si3—C20—H20A	109.5
C5—C4—H4B	109.2	Si3—C20—H20B	109.5
H4A—C4—H4B	107.9	H20A—C20—H20B	109.5
C6—C5—C4	110.6 (6)	Si3—C20—H20C	109.5
C6—C5—H5A	109.5	H20A—C20—H20C	109.5
C4—C5—H5A	109.5	H20B—C20—H20C	109.5
C6—C5—H5B	109.5	Si3—C21—H21A	109.5
C4—C5—H5B	109.5	Si3—C21—H21B	109.5
H5A—C5—H5B	108.1	H21A—C21—H21B	109.5
N2—C6—C5	114.6 (6)	Si3—C21—H21C	109.5
N2—C6—C1	111.3 (5)	H21A—C21—H21C	109.5
C5—C6—C1	109.4 (6)	H21B—C21—H21C	109.5
N2—C6—H6	107.0	Si4—C22—H22A	109.5
C5—C6—H6	107.0	Si4—C22—H22B	109.5
C1—C6—H6	107.0	H22A—C22—H22B	109.5
Si1—C7—H7A	109.5	Si4—C22—H22C	109.5
Si1—C7—H7B	109.5	H22A—C22—H22C	109.5
H7A—C7—H7B	109.5	H22B—C22—H22C	109.5
Si1—C7—H7C	109.5	Si4—C23—H23A	109.5
H7A—C7—H7C	109.5	Si4—C23—H23B	109.5
H7B—C7—H7C	109.5	H23A—C23—H23B	109.5
Si1—C8—H8A	109.5	Si4—C23—H23C	109.5
Si1—C8—H8B	109.5	H23A—C23—H23C	109.5
H8A—C8—H8B	109.5	H23B—C23—H23C	109.5
Si1—C8—H8C	109.5	Si4—C24—H24A	109.5
H8A—C8—H8C	109.5	Si4—C24—H24B	109.5
H8B—C8—H8C	109.5	H24A—C24—H24B	109.5
Si1—C9—H9A	109.5	Si4—C24—H24C	109.5
Si1—C9—H9B	109.5	H24A—C24—H24C	109.5
H9A—C9—H9B	109.5	H24B—C24—H24C	109.5
C8—Si1—N1—C1	76.0 (6)	N1—Zr1—N4—C18	116.0 (4)
C7—Si1—N1—C1	−47.6 (6)	N3—Zr1—N4—C18	−10.5 (4)
C9—Si1—N1—C1	−166.1 (5)	N2—Zr1—N4—Si4	56.9 (4)
C8—Si1—N1—Zr1	−119.5 (5)	N1—Zr1—N4—Si4	−50.0 (4)
C7—Si1—N1—Zr1	116.9 (5)	N3—Zr1—N4—Si4	−176.5 (3)
C9—Si1—N1—Zr1	−1.6 (5)	Si1—N1—C1—C2	−37.8 (7)
N4—Zr1—N1—C1	112.9 (4)	Zr1—N1—C1—C2	155.4 (5)
N2—Zr1—N1—C1	−10.2 (4)	Si1—N1—C1—C6	−162.2 (4)
N3—Zr1—N1—C1	−137.8 (3)	Zr1—N1—C1—C6	31.0 (5)
N4—Zr1—N1—Si1	−53.8 (4)	N1—C1—C2—C3	175.6 (6)
N2—Zr1—N1—Si1	−176.9 (3)	C6—C1—C2—C3	−58.2 (8)
N3—Zr1—N1—Si1	55.5 (4)	C1—C2—C3—C4	55.0 (9)
C12—Si2—N2—C6	−168.6 (5)	C2—C3—C4—C5	−52.8 (9)
C10—Si2—N2—C6	−50.6 (6)	C3—C4—C5—C6	55.8 (9)
C11—Si2—N2—C6	74.4 (7)	Si2—N2—C6—C5	−37.4 (8)
C12—Si2—N2—Zr1	−6.4 (5)	Zr1—N2—C6—C5	157.7 (5)
C10—Si2—N2—Zr1	111.7 (5)	Si2—N2—C6—C1	−162.2 (4)
C11—Si2—N2—Zr1	−123.4 (5)	Zr1—N2—C6—C1	32.9 (6)
N4—Zr1—N2—C6	−140.0 (4)	C4—C5—C6—N2	175.0 (6)
N1—Zr1—N2—C6	−12.9 (4)	C4—C5—C6—C1	−59.2 (8)
N3—Zr1—N2—C6	113.4 (4)	N1—C1—C6—N2	−44.0 (7)
N4—Zr1—N2—Si2	55.2 (4)	C2—C1—C6—N2	−172.0 (5)
N1—Zr1—N2—Si2	−177.8 (4)	N1—C1—C6—C5	−171.7 (5)
N3—Zr1—N2—Si2	−51.4 (4)	C2—C1—C6—C5	60.3 (7)
C20—Si3—N3—C13	77.3 (6)	Si3—N3—C13—C18	−160.6 (4)
C21—Si3—N3—C13	−166.4 (6)	Zr1—N3—C13—C18	34.5 (5)
C19—Si3—N3—C13	−47.4 (6)	Si3—N3—C13—C14	−36.6 (8)
C20—Si3—N3—Zr1	−120.5 (5)	Zr1—N3—C13—C14	158.5 (5)
C21—Si3—N3—Zr1	−4.2 (5)	N3—C13—C14—C15	173.7 (6)
C19—Si3—N3—Zr1	114.7 (5)	C18—C13—C14—C15	−60.3 (8)
N4—Zr1—N3—C13	−13.0 (4)	C13—C14—C15—C16	55.9 (9)
N2—Zr1—N3—C13	110.0 (4)	C14—C15—C16—C17	−53.6 (10)
N1—Zr1—N3—C13	−141.0 (3)	C15—C16—C17—C18	55.5 (10)
N4—Zr1—N3—Si3	−178.1 (4)	Si4—N4—C18—C13	−161.8 (4)
N2—Zr1—N3—Si3	−55.2 (4)	Zr1—N4—C18—C13	31.9 (5)
N1—Zr1—N3—Si3	53.8 (4)	Si4—N4—C18—C17	−39.0 (7)
C24—Si4—N4—C18	76.3 (6)	Zr1—N4—C18—C17	154.8 (5)
C22—Si4—N4—C18	−48.0 (6)	N3—C13—C18—N4	−45.9 (7)
C23—Si4—N4—C18	−165.7 (5)	C14—C13—C18—N4	−172.5 (5)
C24—Si4—N4—Zr1	−120.0 (4)	N3—C13—C18—C17	−171.8 (5)
C22—Si4—N4—Zr1	115.7 (4)	C14—C13—C18—C17	61.7 (7)
C23—Si4—N4—Zr1	−2.0 (5)	C16—C17—C18—N4	176.3 (6)
N2—Zr1—N4—C18	−137.1 (3)	C16—C17—C18—C13	−59.4 (8)