Chloro­[1-(di­methyl­amino­ethyl)­indenyl](tri­phenyl­phosphine)­nickel(II)

The title compound, [η⁵:η⁰–Ind(CH₂)₂NMe₂](PPh₃)NiCl or [NiCl(C₁₃H₁₆N)(C₁₈H₁₅P)], is a precatalyst for the polymerization of olefins. The present structure differs from a previously published polymorph of the same compound in the conformation of the amino tether (disordered over two positions with occupation factors 0.54/0.46) and in the cell parameters.

Key indicators

• Single-crystal X-ray study
• T = 223 K
• Mean [sigma](C-C) = 0.005 Å
• Disorder in main residue
• R factor = 0.060
• wR factor = 0.168
• Data-to-parameter ratio = 14.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           72.66
         From the CIF: _reflns_number_total               5153
         TEST2: Reflns within _diffrn_reflns_theta_max
         Count of symmetry unique reflns         5426
         Completeness (_total/calc)             94.97%
          Alert C: < 95% complete

PLAT_030  Alert C Refined Extinction parameter within range ....       3.20 Sigma

PLAT_301  Alert C Main Residue Disorder ........................      12.00 Perc.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 3 Alert Level C = Please check

---

S1. Comment

A recent review presents the many advantages and possibilities offered by transition-metal complexes of Cp-type ligands bearing a coordinating tether (Müller et al., 2000). Our interest in the structural features and catalytic activities of the nickel indenyl complexes IndNi(PR₃)X (Fontaine et al., 1998; Dubois et al., 2001) prompted us to explore the chemistry of analogous compounds bearing aminoalkyl side chains tethered to the indenyl ligand (Groux et al., 2000). The combination of the title compound, [η⁵:η⁰-Ind(CH₂)₂NMe₂](PPh₃)NiCl, (I), and activators such as AgBF₄ and MAO (methylaluminoxane) catalyses the oligomerization of styrene and the polymerization of norbornene and ethylene (Groux & Zargarian, 2001; further publication in preparation).

The solid-state structure of (I) was determined from a single-crystal X-ray diffraction study carried out on crystals grown from a solution in Et₂O/hexanes at room temperature, and this structure analysis has already been published (Groux et al., 2000). A new batch of crystals was obtained from a solution in CH₂Cl₂/hexanes at 253 K, and this paper reports a new solid-state structure of the same product (a different polymorph), differing only in the conformation of the disordered amino tether. No significant change in the main geometrical parameters is noted. Both crystal structures belong to space group P1; the cell parameters for the first form were: a = 9.215 (2), b = 10.228 (4), c = 16.250 (6) Å; α = 76.60 (3), β = 87.94 (2), γ = 65.43 (2)°; V = 1351.8 (8) ų.

S2. Experimental

The synthesis of (I) has been published elsewhere (Groux et al., 2000). Single crystals suitable for X-ray diffraction study were obtained from a solution of (I) in CH₂Cl₂/hexanes at 253 K.

S3. Refinement

H atoms were constrained with a riding model (SHELXL97 defaults); U_iso(H) was set at 1.5 (methyl) or 1.2 (others) times U_eq of the parent atom. Occupancy factors for the disordered amino tether were initially refined with fixed displacement parameters, then were fixed while displacement parameters were refined; restraints were applied to interatomic distances within the disordered group.

Computing details

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

Figures

Fig. 1. The molecular structure with ellipsoids at the 30% probability level. Disorder is not shown.

Chloro(dimethylamino-1-ethylindenyl)(triphenylphosphine)nickel(II)

Crystal data

[NiCl(C13H16N)(C18H15P)]	Z = 2
Mr = 542.70	F(000) = 568.0
Triclinic, P1	Dx = 1.319 Mg m^−3
a = 9.0763 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 12.8096 (3) Å	Cell parameters from 1005 reflections
c = 13.0012 (3) Å	θ = 3.5–72.0°
α = 83.522 (2)°	µ = 2.61 mm^−1
β = 75.195 (2)°	T = 223 K
γ = 69.2873 (14)°	Block, dark red
V = 1366.51 (5) Å^3	0.65 × 0.65 × 0.34 mm

Data collection

Bruker AXS SMART 2K/Platform diffractometer	5153 independent reflections
Radiation source: normal-focus xray tube	4940 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.084
Detector resolution: 5.5 pixels mm^-1	θmax = 72.7°, θmin = 3.5°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	k = −15→15
Tmin = 0.222, Tmax = 0.411	l = −14→15
16367 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)] = 0.060	H-atom parameters constrained
wR(F^2) = 0.168	w = 1/[σ^2(Fo^2) + (0.1192P)^2 + 0.404P] where P = (Fo^2 + 2Fc^2)/3
S = 1.06	(Δ/σ)max = 0.001
5153 reflections	Δρmax = 0.69 e Å^−3
366 parameters	Δρmin = −0.49 e Å^−3
9 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0016 (5)

Special details

Experimental. X-ray crystallographic data for I were collected from a single-crystal sample, which was mounted on a glass fiber. Data were collected using a Bruker Platform diffractometer, equipped with a Bruker SMART 2 K Charged-Coupled Device (CCD) Area Detector using the program SMART and normal focus sealed tube source graphite monochromated Cu—Kα radiation. The crystal-to-detector distance was 4.908 cm, and the data collection was carried out in 512 x 512 pixel mode, utilizing 4 x 4 pixel binning. The initial unit-cell parameters were determined by a least-squares fit of the angular setting of strong reflections, collected by a 9.0 degree scan in 30 frames over four different parts of the reciprocal space (120 frames total). One complete sphere of data was collected, to better than 0.8 Å resolution. Upon completion of the data collection, the first 101 frames were recollected in order to improve the decay correction analysis.

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. Weighted R-factors wR and all goodnesses of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The observed criterion of F² > σ(F²) is used only for calculating R-factor_obs 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	Occ. (<1)
Ni	0.22031 (4)	0.64414 (3)	0.29066 (3)	0.03511 (17)
Cl	0.04567 (8)	0.70578 (5)	0.43905 (5)	0.0496 (2)
P	0.13087 (6)	0.79216 (4)	0.19304 (4)	0.03057 (18)
C1	0.3225 (3)	0.47700 (18)	0.3491 (2)	0.0408 (5)
C2	0.4408 (3)	0.5179 (2)	0.2855 (2)	0.0473 (6)
H2	0.5275	0.5261	0.3068	0.057*
C3	0.4069 (4)	0.5448 (2)	0.1834 (2)	0.0531 (7)
H3	0.4562	0.5848	0.1288	0.064*
C3A	0.2830 (4)	0.50005 (19)	0.1771 (2)	0.0523 (7)
C4	0.2113 (6)	0.4929 (2)	0.0952 (3)	0.0799 (13)
H4	0.2449	0.5196	0.0259	0.096*
C5	0.0914 (7)	0.4463 (3)	0.1184 (4)	0.0986 (18)
H5	0.0476	0.4372	0.0633	0.118*
C6	0.0333 (6)	0.4122 (3)	0.2207 (4)	0.0873 (14)
H6	−0.0525	0.3840	0.2343	0.105*
C7	0.0994 (4)	0.4191 (2)	0.3035 (3)	0.0608 (8)
H7	0.0589	0.3964	0.3731	0.073*
C7A	0.2272 (3)	0.46035 (18)	0.2812 (2)	0.0454 (6)
C21	0.2225 (3)	0.77885 (17)	0.05072 (18)	0.0339 (4)
C22	0.3858 (3)	0.76734 (19)	0.0155 (2)	0.0401 (5)
H22	0.4444	0.7697	0.0647	0.048*
C23	0.4627 (3)	0.7526 (2)	−0.0908 (2)	0.0463 (6)
H23	0.5727	0.7455	−0.1134	0.056*
C24	0.3775 (4)	0.7482 (2)	−0.1648 (2)	0.0505 (6)
H24	0.4295	0.7372	−0.2371	0.061*
C25	0.2149 (4)	0.7602 (2)	−0.1296 (2)	0.0503 (6)
H25	0.1564	0.7579	−0.1789	0.060*
C26	0.1375 (3)	0.77555 (19)	−0.0236 (2)	0.0411 (5)
H26	0.0270	0.7838	−0.0013	0.049*
C31	−0.0842 (2)	0.82462 (18)	0.20099 (18)	0.0348 (4)
C32	−0.1442 (3)	0.7369 (2)	0.2138 (2)	0.0453 (6)
H32	−0.0755	0.6635	0.2223	0.054*
C33	−0.3038 (3)	0.7569 (2)	0.2140 (2)	0.0521 (6)
H33	−0.3430	0.6970	0.2209	0.062*
C34	−0.4062 (3)	0.8649 (3)	0.2041 (3)	0.0553 (7)
H34	−0.5154	0.8787	0.2051	0.066*
C35	−0.3488 (3)	0.9520 (2)	0.1928 (3)	0.0619 (8)
H35	−0.4191	1.0255	0.1866	0.074*
C36	−0.1873 (3)	0.9326 (2)	0.1905 (3)	0.0501 (6)
H36	−0.1482	0.9927	0.1819	0.060*
C41	0.1485 (2)	0.92225 (17)	0.22430 (19)	0.0340 (5)
C42	0.1784 (3)	1.0002 (2)	0.1450 (2)	0.0431 (5)
H42	0.1880	0.9873	0.0734	0.052*
C43	0.1937 (4)	1.0967 (2)	0.1726 (3)	0.0544 (7)
H43	0.2149	1.1489	0.1191	0.065*
C44	0.1785 (4)	1.1170 (2)	0.2767 (3)	0.0585 (8)
H44	0.1898	1.1826	0.2942	0.070*
C45	0.1468 (4)	1.0418 (2)	0.3552 (3)	0.0580 (7)
H45	0.1343	1.0567	0.4267	0.070*
C46	0.1330 (3)	0.9434 (2)	0.3297 (2)	0.0457 (5)
H46	0.1133	0.8914	0.3837	0.055*
N1_a	0.5097 (11)	0.2517 (8)	0.4309 (12)	0.050 (6)	0.54
C8_a	0.3051 (15)	0.4416 (9)	0.4640 (8)	0.062 (6)	0.54
H8A_a	0.2147	0.4128	0.4860	0.075*	0.54
H8B_a	0.2784	0.5070	0.5066	0.075*	0.54
C9_a	0.4588 (7)	0.3513 (4)	0.4875 (4)	0.0500 (11)	0.54
H9A_a	0.5470	0.3822	0.4701	0.060*	0.54
H9B_a	0.4389	0.3330	0.5639	0.060*	0.54
C10_a	0.4028 (8)	0.1864 (5)	0.4645 (6)	0.0659 (15)	0.54
H10A_a	0.4040	0.1593	0.5372	0.099*	0.54
H10B_a	0.4395	0.1235	0.4182	0.099*	0.54
H10C_a	0.2935	0.2327	0.4607	0.099*	0.54
C11_a	0.6752 (8)	0.1809 (7)	0.4329 (7)	0.080 (2)	0.54
H11A_a	0.6817	0.1579	0.5058	0.120*	0.54
H11B_a	0.7482	0.2224	0.4035	0.120*	0.54
H11C_a	0.7057	0.1155	0.3909	0.120*	0.54
C18_b	0.3063 (17)	0.4404 (8)	0.4649 (6)	0.043 (5)	0.46
H18A_b	0.1939	0.4757	0.5035	0.051*	0.46
H18B_b	0.3749	0.4671	0.4949	0.051*	0.46
C19_b	0.3534 (8)	0.3141 (5)	0.4828 (5)	0.0532 (14)	0.46
H19A_b	0.3455	0.2973	0.5591	0.064*	0.46
H19B_b	0.2744	0.2895	0.4623	0.064*	0.46
N10_b	0.5121 (13)	0.2506 (9)	0.4259 (14)	0.046 (7)	0.46
C110_b	0.6372 (10)	0.2709 (8)	0.4646 (8)	0.081 (2)	0.46
H10D_b	0.6037	0.2781	0.5413	0.121*	0.46
H10E_b	0.6529	0.3393	0.4319	0.121*	0.46
H10F_b	0.7380	0.2090	0.4462	0.121*	0.46
C111_b	0.5371 (15)	0.1316 (6)	0.4428 (8)	0.088 (3)	0.46
H11D_b	0.5203	0.1135	0.5184	0.132*	0.46
H11E_b	0.6468	0.0889	0.4072	0.132*	0.46
H11F_b	0.4609	0.1132	0.4140	0.132*	0.46

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.0312 (3)	0.0276 (2)	0.0440 (3)	−0.00530 (17)	−0.01116 (18)	−0.00065 (16)
Cl	0.0473 (4)	0.0405 (3)	0.0519 (4)	−0.0104 (3)	−0.0012 (3)	−0.0040 (2)
P	0.0234 (3)	0.0253 (3)	0.0436 (3)	−0.0063 (2)	−0.0109 (2)	−0.0020 (2)
C1	0.0413 (12)	0.0266 (10)	0.0504 (14)	−0.0016 (9)	−0.0181 (10)	−0.0001 (9)
C2	0.0344 (11)	0.0354 (12)	0.0638 (16)	−0.0006 (9)	−0.0137 (11)	−0.0001 (10)
C3	0.0513 (15)	0.0323 (12)	0.0523 (15)	0.0049 (10)	−0.0004 (11)	0.0021 (10)
C3A	0.0670 (17)	0.0268 (11)	0.0524 (15)	0.0038 (11)	−0.0221 (13)	−0.0041 (9)
C4	0.125 (3)	0.0361 (14)	0.064 (2)	0.0120 (18)	−0.051 (2)	−0.0061 (12)
C5	0.154 (4)	0.0375 (15)	0.133 (4)	−0.010 (2)	−0.112 (4)	−0.0071 (18)
C6	0.113 (3)	0.0391 (15)	0.142 (4)	−0.0259 (17)	−0.091 (3)	0.0120 (18)
C7	0.0679 (18)	0.0320 (12)	0.092 (2)	−0.0164 (12)	−0.0400 (17)	0.0083 (12)
C7A	0.0540 (14)	0.0247 (10)	0.0566 (15)	−0.0039 (10)	−0.0243 (12)	−0.0022 (9)
C21	0.0301 (10)	0.0268 (9)	0.0433 (12)	−0.0076 (8)	−0.0093 (9)	−0.0004 (8)
C22	0.0329 (11)	0.0343 (11)	0.0507 (13)	−0.0080 (9)	−0.0104 (9)	−0.0011 (9)
C23	0.0386 (12)	0.0328 (11)	0.0580 (15)	−0.0071 (9)	−0.0027 (10)	0.0006 (10)
C24	0.0591 (16)	0.0349 (12)	0.0462 (14)	−0.0072 (11)	−0.0041 (12)	−0.0037 (10)
C25	0.0605 (16)	0.0438 (13)	0.0481 (14)	−0.0126 (12)	−0.0206 (12)	−0.0052 (10)
C26	0.0370 (11)	0.0374 (11)	0.0495 (14)	−0.0092 (9)	−0.0149 (10)	−0.0038 (9)
C31	0.0250 (9)	0.0336 (10)	0.0462 (12)	−0.0084 (8)	−0.0102 (8)	−0.0032 (8)
C32	0.0387 (12)	0.0364 (12)	0.0669 (16)	−0.0155 (10)	−0.0199 (11)	0.0018 (10)
C33	0.0431 (13)	0.0561 (15)	0.0700 (18)	−0.0285 (12)	−0.0209 (12)	0.0031 (12)
C34	0.0293 (11)	0.0659 (17)	0.0763 (19)	−0.0172 (11)	−0.0207 (12)	−0.0008 (14)
C35	0.0307 (13)	0.0453 (14)	0.107 (3)	−0.0025 (11)	−0.0262 (14)	−0.0009 (14)
C36	0.0314 (12)	0.0351 (12)	0.086 (2)	−0.0104 (9)	−0.0207 (12)	0.0017 (11)
C41	0.0214 (9)	0.0258 (9)	0.0557 (13)	−0.0053 (7)	−0.0130 (8)	−0.0046 (8)
C42	0.0395 (12)	0.0338 (11)	0.0604 (15)	−0.0118 (9)	−0.0219 (11)	0.0035 (10)
C43	0.0539 (15)	0.0320 (12)	0.088 (2)	−0.0181 (11)	−0.0347 (14)	0.0093 (12)
C44	0.0565 (16)	0.0303 (12)	0.101 (2)	−0.0134 (11)	−0.0381 (16)	−0.0083 (12)
C45	0.0622 (17)	0.0472 (15)	0.0708 (19)	−0.0169 (13)	−0.0215 (14)	−0.0175 (13)
C46	0.0434 (13)	0.0381 (12)	0.0572 (15)	−0.0139 (10)	−0.0111 (11)	−0.0082 (10)
N1_a	0.056 (10)	0.046 (9)	0.051 (8)	−0.014 (7)	−0.031 (6)	0.012 (5)
C8_a	0.046 (7)	0.040 (8)	0.083 (11)	0.008 (5)	−0.013 (6)	−0.010 (6)
C9_a	0.060 (3)	0.048 (3)	0.052 (3)	−0.019 (2)	−0.029 (2)	0.004 (2)
C10_a	0.068 (4)	0.055 (3)	0.079 (4)	−0.021 (3)	−0.018 (3)	−0.013 (3)
C11_a	0.054 (4)	0.079 (5)	0.096 (5)	0.004 (3)	−0.037 (3)	0.001 (4)
C18_b	0.071 (11)	0.036 (8)	0.025 (6)	−0.019 (7)	−0.023 (6)	0.008 (5)
C19_b	0.051 (3)	0.050 (3)	0.056 (3)	−0.013 (3)	−0.021 (3)	0.019 (3)
N10_b	0.042 (10)	0.042 (10)	0.048 (9)	−0.001 (7)	−0.014 (6)	−0.011 (7)
C110_b	0.051 (4)	0.082 (6)	0.111 (7)	−0.015 (4)	−0.042 (4)	0.015 (5)
C111_b	0.124 (8)	0.041 (4)	0.100 (7)	−0.008 (4)	−0.058 (6)	0.006 (4)

Geometric parameters (Å, º)

Ni—C3	2.025 (3)	C34—C35	1.368 (4)
Ni—C2	2.071 (2)	C34—H34	0.940
Ni—C1	2.147 (2)	C35—C36	1.391 (4)
Ni—Cl	2.1803 (7)	C35—H35	0.940
Ni—P	2.1817 (6)	C36—H36	0.940
Ni—C3A	2.314 (3)	C41—C46	1.389 (4)
Ni—C7A	2.349 (2)	C41—C42	1.396 (3)
P—C31	1.824 (2)	C42—C43	1.387 (3)
P—C21	1.824 (2)	C42—H42	0.940
P—C41	1.828 (2)	C43—C44	1.370 (5)
C1—C2	1.399 (4)	C43—H43	0.940
C1—C7A	1.462 (3)	C44—C45	1.370 (5)
C1—C8_a	1.497 (10)	C44—H44	0.940
C1—C18_b	1.512 (7)	C45—C46	1.394 (4)
C2—C3	1.417 (4)	C45—H45	0.940
C2—H2	0.940	C46—H46	0.940
C3—C3A	1.453 (5)	N1_a—C9_a	1.416 (11)
C3—H3	0.940	N1_a—C10_a	1.451 (10)
C3A—C4	1.409 (4)	N1_a—C11_a	1.460 (10)
C3A—C7A	1.422 (4)	C8_a—C9_a	1.541 (10)
C4—C5	1.372 (7)	C8_a—H8A_a	0.980
C4—H4	0.940	C8_a—H8B_a	0.980
C5—C6	1.382 (8)	C9_a—H9A_a	0.980
C5—H5	0.940	C9_a—H9B_a	0.980
C6—C7	1.383 (5)	C10_a—H10A_a	0.970
C6—H6	0.940	C10_a—H10B_a	0.970
C7—C7A	1.392 (4)	C10_a—H10C_a	0.970
C7—H7	0.940	C11_a—H11A_a	0.970
C21—C22	1.394 (3)	C11_a—H11B_a	0.970
C21—C26	1.394 (3)	C11_a—H11C_a	0.970
C22—C23	1.379 (4)	C18_b—C19_b	1.527 (10)
C22—H22	0.940	C18_b—H18A_b	0.980
C23—C24	1.396 (4)	C18_b—H18B_b	0.980
C23—H23	0.940	C19_b—N10_b	1.431 (11)
C24—C25	1.386 (4)	C19_b—H19A_b	0.980
C24—H24	0.940	C19_b—H19B_b	0.980
C25—C26	1.378 (4)	N10_b—C111_b	1.459 (11)
C25—H25	0.940	N10_b—C110_b	1.464 (13)
C26—H26	0.940	C110_b—H10D_b	0.970
C31—C36	1.384 (3)	C110_b—H10E_b	0.970
C31—C32	1.390 (3)	C110_b—H10F_b	0.970
C32—C33	1.378 (4)	C111_b—H11D_b	0.970
C32—H32	0.940	C111_b—H11E_b	0.970
C33—C34	1.381 (4)	C111_b—H11F_b	0.970
C33—H33	0.940
C3—Ni—C2	40.45 (11)	C36—C31—C32	119.2 (2)
C3—Ni—C1	66.10 (10)	C36—C31—P	122.28 (17)
C2—Ni—C1	38.68 (10)	C32—C31—P	118.43 (17)
C3—Ni—Cl	161.82 (8)	C33—C32—C31	120.5 (2)
C2—Ni—Cl	122.96 (8)	C33—C32—H32	119.77
C1—Ni—Cl	95.94 (7)	C31—C32—H32	119.77
C3—Ni—P	101.65 (8)	C32—C33—C34	120.0 (2)
C2—Ni—P	135.39 (8)	C32—C33—H33	120.02
C1—Ni—P	165.22 (7)	C34—C33—H33	120.02
Cl—Ni—P	96.53 (3)	C35—C34—C33	120.0 (2)
C3—Ni—C3A	38.42 (13)	C35—C34—H34	119.99
C2—Ni—C3A	63.88 (11)	C33—C34—H34	119.99
C1—Ni—C3A	62.66 (9)	C34—C35—C36	120.5 (3)
Cl—Ni—C3A	136.65 (9)	C34—C35—H35	119.75
P—Ni—C3A	102.66 (7)	C36—C35—H35	119.75
C3—Ni—C7A	63.15 (11)	C31—C36—C35	119.8 (2)
C2—Ni—C7A	62.92 (10)	C31—C36—H36	120.10
C1—Ni—C7A	37.60 (9)	C35—C36—H36	120.10
Cl—Ni—C7A	104.72 (7)	C46—C41—C42	119.3 (2)
P—Ni—C7A	130.43 (7)	C46—C41—P	118.95 (18)
C3A—Ni—C7A	35.50 (10)	C42—C41—P	121.73 (18)
C31—P—C21	103.73 (10)	C43—C42—C41	119.6 (3)
C31—P—C41	105.02 (10)	C43—C42—H42	120.22
C21—P—C41	103.31 (10)	C41—C42—H42	120.22
C31—P—Ni	110.41 (7)	C44—C43—C42	120.9 (3)
C21—P—Ni	115.27 (7)	C44—C43—H43	119.57
C41—P—Ni	117.71 (7)	C42—C43—H43	119.57
C2—C1—C7A	108.3 (2)	C45—C44—C43	120.0 (2)
C2—C1—C8_a	127.4 (6)	C45—C44—H44	119.99
C7A—C1—C8_a	123.9 (6)	C43—C44—H44	119.99
C2—C1—C18_b	127.1 (6)	C44—C45—C46	120.4 (3)
C7A—C1—C18_b	124.1 (6)	C44—C45—H45	119.82
C2—C1—Ni	67.73 (13)	C46—C45—H45	119.82
C7A—C1—Ni	78.73 (13)	C41—C46—C45	119.9 (3)
C8_a—C1—Ni	125.2 (4)	C41—C46—H46	120.06
C18_b—C1—Ni	125.7 (4)	C45—C46—H46	120.06
C1—C2—C3	108.0 (2)	C9_a—N1_a—C10_a	114.1 (8)
C1—C2—Ni	73.59 (14)	C9_a—N1_a—C11_a	112.7 (9)
C3—C2—Ni	68.04 (14)	C10_a—N1_a—C11_a	109.5 (8)
C1—C2—H2	126.00	C1—C8_a—C9_a	113.3 (7)
C3—C2—H2	126.00	C1—C8_a—H8A_a	108.9
Ni—C2—H2	123.94	C9_a—C8_a—H8A_a	108.9
C2—C3—C3A	108.5 (2)	C1—C8_a—H8B_a	108.9
C2—C3—Ni	71.51 (15)	C9_a—C8_a—H8B_a	108.9
C3A—C3—Ni	81.58 (17)	H8A_a—C8_a—H8B_a	107.7
C2—C3—H3	125.77	N1_a—C9_a—C8_a	114.4 (8)
C3A—C3—H3	125.77	N1_a—C9_a—H9A_a	108.7
Ni—C3—H3	113.36	C8_a—C9_a—H9A_a	108.7
C4—C3A—C7A	119.0 (3)	N1_a—C9_a—H9B_a	108.7
C4—C3A—C3	134.2 (3)	C8_a—C9_a—H9B_a	108.7
C7A—C3A—C3	106.7 (2)	H9A_a—C9_a—H9B_a	107.6
C4—C3A—Ni	130.24 (19)	N1_a—C10_a—H10A_a	109.5
C7A—C3A—Ni	73.62 (14)	N1_a—C10_a—H10B_a	109.5
C3—C3A—Ni	60.00 (14)	H10A_a—C10_a—H10B_a	109.5
C5—C4—C3A	118.6 (4)	N1_a—C10_a—H10C_a	109.5
C5—C4—H4	120.7	H10A_a—C10_a—H10C_a	109.5
C3A—C4—H4	120.7	H10B_a—C10_a—H10C_a	109.5
C4—C5—C6	121.9 (3)	N1_a—C11_a—H11A_a	109.5
C4—C5—H5	119.1	N1_a—C11_a—H11B_a	109.5
C6—C5—H5	119.1	H11A_a—C11_a—H11B_a	109.5
C5—C6—C7	121.1 (4)	N1_a—C11_a—H11C_a	109.5
C5—C6—H6	119.5	H11A_a—C11_a—H11C_a	109.5
C7—C6—H6	119.5	H11B_a—C11_a—H11C_a	109.5
C6—C7—C7A	118.3 (4)	C1—C18_b—C19_b	113.7 (7)
C6—C7—H7	120.8	C1—C18_b—H18A_b	108.8
C7A—C7—H7	120.84	C19_b—C18_b—H18A_b	108.8
C7—C7A—C3A	120.9 (3)	C1—C18_b—H18B_b	108.8
C7—C7A—C1	131.7 (3)	C19_b—C18_b—H18B_b	108.8
C3A—C7A—C1	107.4 (2)	H18A_b—C18_b—H18B_b	107.7
C7—C7A—Ni	129.10 (19)	N10_b—C19_b—C18_b	115.2 (8)
C3A—C7A—Ni	70.88 (14)	N10_b—C19_b—H19A_b	108.5
C1—C7A—Ni	63.67 (12)	C18_b—C19_b—H19A_b	108.5
C22—C21—C26	118.7 (2)	N10_b—C19_b—H19B_b	108.5
C22—C21—P	118.54 (18)	C18_b—C19_b—H19B_b	108.5
C26—C21—P	122.70 (18)	H19A_b—C19_b—H19B_b	107.5
C23—C22—C21	120.9 (2)	C19_b—N10_b—C111_b	109.9 (10)
C23—C22—H22	119.54	C19_b—N10_b—C110_b	111.3 (10)
C21—C22—H22	119.54	C111_b—N10_b—C110_b	106.6 (11)
C22—C23—C24	120.2 (2)	N10_b—C110_b—H10D_b	109.5
C22—C23—H23	119.91	N10_b—C110_b—H10E_b	109.5
C24—C23—H23	119.91	H10D_b—C110_b—H10E_b	109.5
C25—C24—C23	118.8 (3)	N10_b—C110_b—H10F_b	109.5
C25—C24—H24	120.60	H10D_b—C110_b—H10F_b	109.5
C23—C24—H24	120.60	H10E_b—C110_b—H10F_b	109.5
C26—C25—C24	121.2 (3)	N10_b—C111_b—H11D_b	109.5
C26—C25—H25	119.41	N10_b—C111_b—H11E_b	109.5
C24—C25—H25	119.41	H11D_b—C111_b—H11E_b	109.5
C25—C26—C21	120.2 (2)	N10_b—C111_b—H11F_b	109.5
C25—C26—H26	119.90	H11D_b—C111_b—H11F_b	109.5
C21—C26—H26	119.90	H11E_b—C111_b—H11F_b	109.5
C3—Ni—P—C31	124.71 (13)	C5—C6—C7—C7A	−0.5 (5)
C2—Ni—P—C31	150.88 (14)	C6—C7—C7A—C3A	3.3 (4)
C1—Ni—P—C31	91.9 (3)	C6—C7—C7A—C1	−179.4 (3)
Cl—Ni—P—C31	−55.50 (8)	C6—C7—C7A—Ni	93.0 (4)
C3A—Ni—P—C31	85.38 (12)	C4—C3A—C7A—C7	−2.6 (4)
C7A—Ni—P—C31	60.19 (13)	C3—C3A—C7A—C7	175.6 (2)
C3—Ni—P—C21	7.60 (13)	Ni—C3A—C7A—C7	124.8 (2)
C2—Ni—P—C21	33.77 (14)	C4—C3A—C7A—C1	179.5 (2)
C1—Ni—P—C21	−25.2 (3)	C3—C3A—C7A—C1	−2.3 (3)
Cl—Ni—P—C21	−172.61 (8)	Ni—C3A—C7A—C1	−53.09 (16)
C3A—Ni—P—C21	−31.72 (12)	C4—C3A—C7A—Ni	−127.4 (2)
C7A—Ni—P—C21	−56.92 (13)	C3—C3A—C7A—Ni	50.77 (16)
C3—Ni—P—C41	−114.78 (13)	C2—C1—C7A—C7	178.1 (3)
C2—Ni—P—C41	−88.61 (14)	C8_a—C1—C7A—C7	5.0 (6)
C1—Ni—P—C41	−147.6 (3)	C18_b—C1—C7A—C7	5.6 (6)
Cl—Ni—P—C41	65.01 (8)	Ni—C1—C7A—C7	−120.1 (3)
C3A—Ni—P—C41	−154.10 (12)	C2—C1—C7A—C3A	−4.3 (3)
C7A—Ni—P—C41	−179.30 (12)	C8_a—C1—C7A—C3A	−177.4 (5)
C3—Ni—C1—C2	38.89 (18)	C18_b—C1—C7A—C3A	−176.9 (5)
Cl—Ni—C1—C2	−138.18 (15)	Ni—C1—C7A—C3A	57.45 (17)
P—Ni—C1—C2	74.4 (3)	C2—C1—C7A—Ni	−61.77 (15)
C3A—Ni—C1—C2	81.53 (18)	C8_a—C1—C7A—Ni	125.1 (5)
C7A—Ni—C1—C2	115.3 (2)	C18_b—C1—C7A—Ni	125.7 (6)
C3—Ni—C1—C7A	−76.46 (18)	C3—Ni—C7A—C7	−151.4 (3)
C2—Ni—C1—C7A	−115.3 (2)	C2—Ni—C7A—C7	163.0 (3)
Cl—Ni—C1—C7A	106.47 (15)	C1—Ni—C7A—C7	123.6 (3)
P—Ni—C1—C7A	−41.0 (4)	Cl—Ni—C7A—C7	43.1 (3)
C3A—Ni—C1—C7A	−33.81 (16)	P—Ni—C7A—C7	−69.1 (3)
C3—Ni—C1—C8_a	159.8 (8)	C3A—Ni—C7A—C7	−114.8 (3)
C2—Ni—C1—C8_a	120.9 (8)	C3—Ni—C7A—C3A	−36.63 (18)
Cl—Ni—C1—C8_a	−17.3 (7)	C2—Ni—C7A—C3A	−82.27 (18)
P—Ni—C1—C8_a	−164.7 (7)	C1—Ni—C7A—C3A	−121.6 (2)
C3A—Ni—C1—C8_a	−157.6 (8)	Cl—Ni—C7A—C3A	157.90 (15)
C7A—Ni—C1—C8_a	−123.7 (8)	P—Ni—C7A—C3A	45.67 (19)
C3—Ni—C1—C18_b	159.5 (7)	C3—Ni—C7A—C1	85.01 (18)
C2—Ni—C1—C18_b	120.6 (7)	C2—Ni—C7A—C1	39.37 (16)
Cl—Ni—C1—C18_b	−17.6 (7)	Cl—Ni—C7A—C1	−80.46 (15)
P—Ni—C1—C18_b	−165.0 (7)	P—Ni—C7A—C1	167.31 (12)
C3A—Ni—C1—C18_b	−157.9 (7)	C3A—Ni—C7A—C1	121.6 (2)
C7A—Ni—C1—C18_b	−124.1 (7)	C31—P—C21—C22	172.27 (17)
C7A—C1—C2—C3	9.4 (3)	C41—P—C21—C22	62.89 (19)
C8_a—C1—C2—C3	−177.8 (5)	Ni—P—C21—C22	−66.91 (18)
C18_b—C1—C2—C3	−178.3 (6)	C31—P—C21—C26	−10.2 (2)
Ni—C1—C2—C3	−59.63 (16)	C41—P—C21—C26	−119.57 (19)
C7A—C1—C2—Ni	69.01 (16)	Ni—P—C21—C26	110.63 (18)
C8_a—C1—C2—Ni	−118.2 (5)	C26—C21—C22—C23	−0.2 (3)
C18_b—C1—C2—Ni	−118.7 (6)	P—C21—C22—C23	177.43 (17)
C3—Ni—C2—C1	−117.8 (2)	C21—C22—C23—C24	−0.4 (4)
Cl—Ni—C2—C1	52.23 (18)	C22—C23—C24—C25	0.8 (4)
P—Ni—C2—C1	−159.52 (12)	C23—C24—C25—C26	−0.4 (4)
C3A—Ni—C2—C1	−78.12 (17)	C24—C25—C26—C21	−0.2 (4)
C7A—Ni—C2—C1	−38.26 (15)	C22—C21—C26—C25	0.5 (3)
C1—Ni—C2—C3	117.8 (2)	P—C21—C26—C25	−176.99 (18)
Cl—Ni—C2—C3	170.00 (15)	C21—P—C31—C36	−85.9 (2)
P—Ni—C2—C3	−41.7 (2)	C41—P—C31—C36	22.2 (2)
C3A—Ni—C2—C3	39.66 (17)	Ni—P—C31—C36	150.1 (2)
C7A—Ni—C2—C3	79.51 (18)	C21—P—C31—C32	91.5 (2)
C1—C2—C3—C3A	−10.9 (3)	C41—P—C31—C32	−160.4 (2)
Ni—C2—C3—C3A	−74.07 (18)	Ni—P—C31—C32	−32.6 (2)
C1—C2—C3—Ni	63.18 (17)	C36—C31—C32—C33	1.2 (4)
C1—Ni—C3—C2	−37.22 (15)	P—C31—C32—C33	−176.2 (2)
Cl—Ni—C3—C2	−27.8 (4)	C31—C32—C33—C34	−1.6 (4)
P—Ni—C3—C2	151.48 (15)	C32—C33—C34—C35	0.7 (5)
C3A—Ni—C3—C2	−112.8 (2)	C33—C34—C35—C36	0.5 (5)
C7A—Ni—C3—C2	−78.89 (16)	C32—C31—C36—C35	0.0 (4)
C2—Ni—C3—C3A	112.8 (2)	P—C31—C36—C35	177.3 (3)
C1—Ni—C3—C3A	75.55 (15)	C34—C35—C36—C31	−0.8 (5)
Cl—Ni—C3—C3A	84.9 (4)	C31—P—C41—C46	89.50 (19)
P—Ni—C3—C3A	−95.75 (14)	C21—P—C41—C46	−162.09 (18)
C7A—Ni—C3—C3A	33.88 (14)	Ni—P—C41—C46	−33.8 (2)
C2—C3—C3A—C4	−174.2 (3)	C31—P—C41—C42	−91.06 (19)
Ni—C3—C3A—C4	118.6 (3)	C21—P—C41—C42	17.3 (2)
C2—C3—C3A—C7A	8.1 (3)	Ni—P—C41—C42	145.65 (16)
Ni—C3—C3A—C7A	−59.11 (18)	C46—C41—C42—C43	0.6 (3)
C2—C3—C3A—Ni	67.21 (17)	P—C41—C42—C43	−178.79 (19)
C3—Ni—C3A—C4	−124.5 (4)	C41—C42—C43—C44	−0.6 (4)
C2—Ni—C3A—C4	−166.3 (4)	C42—C43—C44—C45	−0.3 (4)
C1—Ni—C3A—C4	150.2 (4)	C43—C44—C45—C46	1.2 (5)
Cl—Ni—C3A—C4	82.4 (4)	C42—C41—C46—C45	0.2 (4)
P—Ni—C3A—C4	−31.6 (4)	P—C41—C46—C45	179.7 (2)
C7A—Ni—C3A—C4	114.4 (4)	C44—C45—C46—C41	−1.2 (4)
C3—Ni—C3A—C7A	121.1 (2)	C2—C1—C8_a—C9_a	−55.5 (11)
C2—Ni—C3A—C7A	79.29 (17)	C7A—C1—C8_a—C9_a	116.3 (9)
C1—Ni—C3A—C7A	35.78 (15)	C18_b—C1—C8_a—C9_a	5 (100)
Cl—Ni—C3A—C7A	−32.0 (2)	Ni—C1—C8_a—C9_a	−143.0 (6)
P—Ni—C3A—C7A	−146.08 (14)	C10_a—N1_a—C9_a—C8_a	−69.4 (12)
C2—Ni—C3A—C3	−41.77 (16)	C11_a—N1_a—C9_a—C8_a	164.9 (9)
C1—Ni—C3A—C3	−85.28 (17)	C1—C8_a—C9_a—N1_a	−59.0 (13)
Cl—Ni—C3A—C3	−153.08 (14)	C2—C1—C18_b—C19_b	−107.2 (8)
P—Ni—C3A—C3	92.85 (15)	C7A—C1—C18_b—C19_b	64.0 (10)
C7A—Ni—C3A—C3	−121.1 (2)	C8_a—C1—C18_b—C19_b	133 (100)
C7A—C3A—C4—C5	−0.9 (4)	Ni—C1—C18_b—C19_b	165.2 (5)
C3—C3A—C4—C5	−178.4 (3)	C1—C18_b—C19_b—N10_b	55.0 (13)
Ni—C3A—C4—C5	−93.6 (4)	C18_b—C19_b—N10_b—C111_b	−175.4 (9)
C3A—C4—C5—C6	3.7 (5)	C18_b—C19_b—N10_b—C110_b	66.9 (13)
C4—C5—C6—C7	−3.1 (6)