Di­bromo{N-[2-(di­phenyl­phosphino)­benzyl­idene]-2,6-diiso­propyl­aniline-[kappa]²N,P}nickel

In the title compound, [NiBr₂(C₃₁H₃₂NP)], (I), the second reported example of a nickel-imino­phosphine N,P-chelate in which the Ni atom has tetrahedral coordination, the Ni coordination is distorted as a consequence of the N-Ni-P chelate bite angle of 91.07 (6)° compensated by the Br-­Ni-­Br angle of 126.385 (18)°. In (I) and its analogue, viz. dichloro{[2-(4-isobutyloxazol-2-yl)phenyl]diphenylphos­phine-N,P}nickel(II), the Ni-N and Ni-P distances are greater and the N-Ni-P ligand bite angles smaller than those observed in a series of related complexes with square-planar nickel.

S1. Comment

Arising from the search for good catalysts, the Cambridge Structural Database (CSD; Allen & Kennard, 1993), accessible at the Chemical Database Service of the EPSRC (Fletcher et al., 1996), contains a number of entries for the structures of transition metal complexes (especially Ni and Pd) of α-diimines, RN═CR'—CR'═NR'', and bisphosphines, R₂P—X—PR₂ [e.g. X = (CH₂)_n for n = 1, 2, 3 etc.]. Until recently, relatively few structural studies of mixed N,P-chelating ligands, such as the iminophosphines, o-R₂PC₆H₄—CH═NR [represented as (N,P) below], have been reported. The majority of these are for Pd complexes typified by [PdRX(N,P)], [Pd(COR)X(N,P)], [PdR(N,P)L_n][X] and [Pd(N,P)L_n][X]₂ (Bandoli et al., 2000; Crociani et al., 1999; Reddy et al., 2001; Rülke et al., 1996; Sanchez et al., 1999; Sanchez, Momblona et al., 2001; Sanchez, Serrano et al., 2001; Watkins et al., 2000). At the time of writing, there are by comparison relatively few structural reports of iminophosphine complexes of nickel. Characterization of nickel–iminophosphine complexes by IR and NMR spectroscopic methods has, however, been reported, e.g. for [Ni(C₆F₅)₂(o-Ph₂PC₆H₄CH═NR)] (R = Me, Et, Pr, ⁱPr, ^tBu, Ph or NHMe) (Sanchez et al., 1998).

Considering only those nickel–iminophosphine complexes for which coordinate data are currently available in the CSD, the structure of the title compound, (I) (Fig. 1), may thus be compared (Table 1) with those of dichloro[2-(4-isobutyloxazol-2-yl)phenyldiphenylphosphine-N,P]nickel(II) (PATQEG; Lloyd-Jones & Butts, 1998), (II), and further with the group comprising [2-(diphenylphosphino)benzaldehyde semithiocarbazonato]pyridinenickel(II) nitrate, (RUTLEX; Leovac et al., 1996), (III), chloro[3-hydroxy-3-phenyl-N-[2-(diphenylphosphino)benzylidene]-2- propylamine]nickel chloride ethanol solvate, (IV), and chloro[2-oxy-N-(2-diphenylphosphino)benzylidene]anilinenickel, (V) (GONPAA and GONQAB, respectively; Bhattacharyya et al., 1998) and chloro[2-(diphenylphopsphino)benzaldehyde benzoylhydrazone]nickel(II), (MALBEG; Bacci et al., 2000), (VI).

The coordination of the Ni atom in (III)–(VI) is square planar, as is the case for Pd in all of the known four-coordinate palladium–iminophosphine chelates. In contrast, the Ni atom in (I) and (II) has a distorted tetrahedral environment, the distortion being brought about to a great extent by the ligand bite angles and compensated for by increased X—Ni—X angles (X = Br or Cl). From this limited evidence it is tempting to associate the tetrahedral coordination of Ni in (I) and (II) with the dihalide complexes. This holds true also for the α-diimine complex [NiBr₂(^tBuN═CHCH═N^tBu)] (CESWEC; Jameson et al., 1984). However, the square-planar coordination of nickel in the bisphosphine complexes [NiBr₂(Ph₂PCH₂CH₂PPh₂)] (SAHYUC; Rahn et al., 1989) and [NiCl₂(Ph₂PCH₂CH₂PPh₂)] forms A, B and C (Davison et al., 2001, and references therein) tends to negate this argument although the size of the chelate rings [six-membered in (I)–(VI) and five-membered in the remainder] may be of significance here. Of greater significance is the fact that the X atoms (Table 1) of (III)–(VI) not only bind to the Ni atom trans to the iminophosphine P atom, but are also part of a substituent on the iminophosphine N atom. As a result, in addition to the six-membered iminophosphine N,P-chelate ring, a five-membered X,N-chelate ring is also formed and the ligands are now tridentate in nature. The nature of the C═N imine bond is expected to have a constraining effect upon the relative orientation of the chelate rings and the angles between their least-squares planes, IP2 (Table 2), ranging from 3.4 (13) to 28.76 (15)°, suggests that to some extent this is so. The near planar arrangement of the chelate rings and the bite angles of the five- and six-membered chelates, X—Ni—N 89.03 (17)–91.98 (9)° and N—Ni—P 91.47 (10)–95.14 (12)° all favour square-planar coordination of nickel. The evidence presented above does however suggest that the tetrahedral configuration is favoured when Ni forms a dihalo complex with a bidentate ligand with an imine N atom as at least one of the donor atoms. According to Greenwood & Earnshaw (1997), four-coordinate nickel complexes are for the most part square planar and diamagnetic, but tetrahedral paramagnetic complexes also occur and there are no firm criteria for predicting which arrangement will occur in a given case.

In Table 1, it is clear that the Ni—N and Ni—P bond lengths for (I) and (II) are very similar but significantly longer than those found in (III)–(VI). As expected, the bite angles of the iminophosphine ligands or ligand fragments show comparatively little variation. It is noted, however, that the lowest values are associated with (I) and (II), and may therefore be associated with the comparatively long Ni—N and Ni—P bonds. As noted above, the bite angles are in any case much better suited to square-planar coordination of nickel than to tetrahedral coordination.

The six-membered chelate rings in (I)–(VI) are all puckered, but to varying degrees. The Cremer & Pople (1975) puckering parameters, along with selected interplanar angles, are presented in Table 2. In terms of the puckering amplitudes, the compounds fall into three categories, with (I) and (II) being the most puckered, (III)–(V) forming an intermediate group and (VI) the least puckered. This classification extends to the manner in which substituent atoms are disposed around the chelate rings. Thus, in (I) and (II) there are two axial groups, the halide Y in Table 1 (Br2 or Cl2) and one of the phenyl groups attached to P [e.g. C26–C31 of (I)], and all other substituents are equatorial. In (III)–(V) the only axial substituent is one of the phenyl rings attached to P. Here, again, (VI) constitutes a special case because the only substituents which might not be considered to be in equatorial sites are the two phenyl rings attached to P, but the comparatively planar nature of the chelate ring renders their equatorial or axial status indeterminate. The same classification is also reflected in a variation of the angle between the six-membered N,P-chelate ring and the benzene ring of the ligand, IP1 (Table 2).

Related literature

For related literature, see: Allen & Kennard (1993); Bandoli et al. (2000); Bhattacharyya et al. (1998); Cremer & Pople (1975); Crociani et al. (1999); Davison et al. (2001); Fletcher et al. (1996); Greenwood & Earnshaw (1997); Jameson et al. (1984); Leovac et al. (1996); Lloyd-Jones & Butts (1998); Rülke et al. (1996); Rahn et al. (1989); Reddy et al. (2001); Sanchez et al. (1998, 1999); Sanchez, Momblona, Perez, Lopez, Serrano, Liu & Sanz (2001); Sanchez, Serrano, Momblona, Ruiz, Garcia, Perez, Lopez, Chaloner & Hitchcock (2001); Watkins et al. (2000).

S2. Experimental

The ligand 2,6-ⁱPr₂C₆H₃N═CHC₆H₄PPh₂-2, (VII), was prepared by the addition of 2,6-diisopropylaniline (0.9 ml, 4.3 mmol), formic acid (ca 0.2 ml of a 88% aqueous solution) and anhydrous sodium sulfate to a solution of 2-(diphenylphosphinyl)benzaldehyde (1.16 g, 4.0 mmol) in CH₂Cl₂ (30 ml). The reaction mixture was stirred for 24 h, the solvent removed and the crude product column chromatographed on silica gel with CHCl₃ as eluent affording (VII) as a yellow solid (1.44 g, 80% yield). IR (CsI): ν(C═N) 1630 cm^-1; ¹H NMR (CDCl₃, 200 MHz, p.p.m.): δ 0.91 (d, 6H, J = 6.8 Hz, Me), 2.70 (sept, 1H, J = 6.8 Hz, CHMe₂), 6.7–8.2 (m, 5H, phenyl-H), 8.85 (d, 1H, J_H—P = 5.5 Hz, N═CH); ³¹P{¹H} NMR (CDCl₃, 122 MHz, p.p.m.): δ -15.0. A solution of (VII) (0.33 g, 0.74 mmol) in CH₂Cl₂ (10 ml) was added to a suspension of anhydrous nickel bromide (0.15 g, 0.71 mmol) in CH₂Cl₂/MeCN (3:1, v/v). The resulting dark-red solution was stirred for 3 h at room temperature, the solvent removed under reduced pressure and the solid product washed several times with dry hexane to afford (I) in 98% yield. Crystals suitable for X-ray analysis were obtained from CH₂Cl₂/hexane. IR (CsI): ν(C═N) 1611 cm^-1.

S3. Refinement

In the final stages of refinement, aryl, methyl and tertiary] H atoms were introduced in calculated positions with C—H distances of 0.95, 0.98 and 1.00 Å, respectively, and refined as riding with U_iso = 1.2U_eq, 1.5U_eq 1.2U_eq, respectively.

Computing details

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); 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. The molecule of (I) showing the atom-labelling scheme. Non-H atoms are shown as 50% ellipsoids and H atoms have been omitted for clarity.

Dibromo{N-[2-(diphenylphosphino)benzylidene]-2,6-diisopropylaniline- κ²N,P}nickel

Crystal data

[NiBr2(C31H32NP)]	F(000) = 1352
Mr = 668.08	Dx = 1.515 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.6639 (2) Å	Cell parameters from 13744 reflections
b = 14.4016 (3) Å	θ = 2.9–27.5°
c = 19.7744 (4) Å	µ = 3.47 mm^−1
β = 105.2700 (13)°	T = 120 K
V = 2929.68 (10) Å^3	Cube, dark red
Z = 4	0.18 × 0.18 × 0.17 mm

Data collection

Enraf Nonius KappaCCD area-detector diffractometer	6683 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	4970 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.057
Detector resolution: 9.091 pixels mm^-1	θmax = 27.5°, θmin = 3.0°
ϕ and ω scans to fill the Ewald sphere	h = −13→13
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997)	k = −17→18
Tmin = 0.843, Tmax = 0.947	l = −25→25
22746 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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.083	H-atom parameters constrained
S = 1.05	w = 1/[σ^2(Fo^2) + (0.0359P)^2] where P = (Fo^2 + 2Fc^2)/3
6683 reflections	(Δ/σ)max = 0.001
329 parameters	Δρmax = 0.48 e Å^−3
0 restraints	Δρmin = −0.70 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

H in calculated positions and refined with a riding model.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Ni	0.37422 (3)	0.89318 (2)	0.238242 (16)	0.01763 (9)
Br1	0.53546 (3)	0.81495 (2)	0.321789 (14)	0.02692 (9)
Br2	0.15675 (3)	0.84497 (2)	0.192938 (14)	0.02649 (9)
N	0.3743 (2)	1.02785 (15)	0.26413 (10)	0.0179 (5)
C1	0.4094 (3)	1.05294 (18)	0.33859 (13)	0.0184 (6)
C2	0.3123 (3)	1.05027 (19)	0.37424 (13)	0.0195 (6)
C3	0.3476 (3)	1.07687 (19)	0.44474 (13)	0.0229 (6)
H3	0.2844	1.0750	0.4708	0.028*
C4	0.4715 (3)	1.10560 (19)	0.47717 (14)	0.0242 (6)
H4	0.4927	1.1247	0.5248	0.029*
C5	0.5654 (3)	1.10683 (19)	0.44065 (13)	0.0225 (6)
H5	0.6507	1.1273	0.4635	0.027*
C6	0.5371 (3)	1.07855 (18)	0.37077 (13)	0.0189 (6)
C7	0.1718 (3)	1.02452 (19)	0.33988 (14)	0.0224 (6)
H7	0.1662	1.0041	0.2908	0.027*
C8	0.0852 (3)	1.1104 (2)	0.33587 (15)	0.0306 (7)
H8A	0.0836	1.1290	0.3833	0.046*
H8B	−0.0032	1.0957	0.3084	0.046*
H8C	0.1200	1.1613	0.3134	0.046*
C9	0.1251 (3)	0.9442 (2)	0.37744 (15)	0.0346 (7)
H9A	0.1813	0.8901	0.3782	0.052*
H9B	0.0355	0.9283	0.3526	0.052*
H9C	0.1286	0.9627	0.4256	0.052*
C10	0.6437 (3)	1.07801 (19)	0.33256 (14)	0.0227 (6)
H10	0.6112	1.0413	0.2885	0.027*
C11	0.6720 (3)	1.1761 (2)	0.31171 (17)	0.0365 (8)
H11A	0.5939	1.2018	0.2792	0.055*
H11B	0.7430	1.1743	0.2888	0.055*
H11C	0.6970	1.2152	0.3537	0.055*
C12	0.7667 (3)	1.0306 (2)	0.37582 (16)	0.0356 (8)
H12A	0.8262	1.0198	0.3464	0.053*
H12B	0.7438	0.9711	0.3934	0.053*
H12C	0.8090	1.0705	0.4154	0.053*
C13	0.3346 (3)	1.09566 (19)	0.22147 (13)	0.0206 (6)
H13	0.3341	1.1553	0.2419	0.025*
C14	0.2898 (3)	1.09103 (18)	0.14439 (13)	0.0195 (6)
C15	0.3258 (2)	1.02324 (18)	0.10111 (13)	0.0180 (6)
C16	0.2715 (3)	1.0285 (2)	0.02944 (13)	0.0236 (6)
H16	0.2971	0.9850	−0.0005	0.028*
C17	0.1800 (3)	1.0965 (2)	0.00018 (14)	0.0295 (7)
H17	0.1411	1.0971	−0.0489	0.035*
C18	0.1460 (3)	1.1625 (2)	0.04224 (15)	0.0309 (7)
H18	0.0841	1.2090	0.0224	0.037*
C19	0.2030 (3)	1.1610 (2)	0.11421 (15)	0.0289 (7)
H19	0.1824	1.2082	0.1430	0.035*
P	0.43589 (6)	0.92893 (5)	0.13980 (3)	0.01647 (15)
C20	0.4234 (3)	0.84454 (18)	0.06983 (13)	0.0186 (6)
C21	0.5311 (3)	0.81881 (19)	0.04632 (13)	0.0227 (6)
H21	0.6136	0.8458	0.0670	0.027*
C22	0.5183 (3)	0.7540 (2)	−0.00718 (14)	0.0299 (7)
H22	0.5924	0.7356	−0.0221	0.036*
C23	0.3982 (3)	0.7165 (2)	−0.03860 (14)	0.0310 (7)
H23	0.3892	0.6733	−0.0758	0.037*
C24	0.2908 (3)	0.7417 (2)	−0.01608 (13)	0.0293 (7)
H24	0.2082	0.7159	−0.0383	0.035*
C25	0.3025 (3)	0.80427 (19)	0.03870 (13)	0.0234 (6)
H25	0.2288	0.8197	0.0549	0.028*
C26	0.6004 (2)	0.97306 (19)	0.15681 (12)	0.0183 (6)
C27	0.6316 (3)	1.0592 (2)	0.13392 (13)	0.0240 (6)
H27	0.5646	1.1002	0.1102	0.029*
C28	0.7609 (3)	1.0852 (2)	0.14586 (14)	0.0311 (7)
H28	0.7820	1.1448	0.1315	0.037*
C29	0.8587 (3)	1.0255 (2)	0.17816 (14)	0.0303 (7)
H29	0.9469	1.0430	0.1843	0.036*
C30	0.8293 (3)	0.9399 (2)	0.20177 (14)	0.0290 (7)
H30	0.8972	0.8989	0.2243	0.035*
C31	0.7008 (3)	0.9140 (2)	0.19263 (13)	0.0240 (6)
H31	0.6807	0.8563	0.2106	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ni	0.01971 (19)	0.01514 (18)	0.01874 (17)	−0.00005 (14)	0.00631 (13)	0.00068 (14)
Br1	0.02717 (17)	0.02666 (17)	0.02424 (15)	0.00301 (12)	0.00202 (11)	0.00561 (12)
Br2	0.01957 (16)	0.02659 (17)	0.03423 (17)	−0.00351 (12)	0.00875 (12)	−0.00290 (12)
N	0.0147 (11)	0.0196 (12)	0.0199 (11)	−0.0005 (9)	0.0055 (9)	−0.0026 (10)
C1	0.0233 (15)	0.0132 (13)	0.0183 (13)	0.0022 (11)	0.0051 (10)	−0.0017 (11)
C2	0.0203 (14)	0.0181 (14)	0.0197 (13)	0.0020 (11)	0.0043 (10)	−0.0004 (11)
C3	0.0259 (16)	0.0243 (15)	0.0207 (13)	0.0022 (12)	0.0099 (11)	−0.0013 (12)
C4	0.0265 (16)	0.0237 (16)	0.0216 (14)	0.0013 (12)	0.0051 (12)	−0.0058 (12)
C5	0.0210 (15)	0.0209 (15)	0.0242 (14)	−0.0020 (12)	0.0038 (11)	−0.0046 (12)
C6	0.0217 (15)	0.0125 (13)	0.0231 (13)	−0.0006 (11)	0.0069 (11)	−0.0014 (11)
C7	0.0217 (15)	0.0252 (16)	0.0223 (13)	−0.0017 (12)	0.0093 (11)	−0.0019 (12)
C8	0.0218 (16)	0.0329 (18)	0.0357 (16)	0.0031 (13)	0.0052 (13)	−0.0021 (14)
C9	0.0328 (18)	0.0347 (19)	0.0368 (17)	−0.0093 (15)	0.0101 (14)	0.0030 (15)
C10	0.0200 (15)	0.0251 (16)	0.0245 (14)	−0.0032 (12)	0.0083 (11)	−0.0081 (12)
C11	0.0383 (19)	0.0327 (19)	0.0438 (19)	−0.0060 (15)	0.0202 (15)	−0.0011 (15)
C12	0.0235 (17)	0.043 (2)	0.0416 (18)	−0.0010 (15)	0.0117 (14)	−0.0078 (16)
C13	0.0210 (15)	0.0161 (14)	0.0262 (14)	0.0000 (11)	0.0088 (11)	−0.0021 (12)
C14	0.0193 (14)	0.0172 (14)	0.0221 (13)	−0.0003 (11)	0.0058 (11)	0.0011 (11)
C15	0.0160 (14)	0.0168 (14)	0.0221 (13)	0.0003 (11)	0.0063 (10)	0.0024 (11)
C16	0.0264 (16)	0.0237 (16)	0.0217 (14)	0.0024 (12)	0.0079 (11)	0.0010 (12)
C17	0.0315 (17)	0.0340 (18)	0.0212 (14)	0.0063 (14)	0.0037 (12)	0.0076 (13)
C18	0.0300 (17)	0.0275 (17)	0.0350 (17)	0.0119 (14)	0.0083 (13)	0.0106 (14)
C19	0.0330 (18)	0.0231 (16)	0.0315 (16)	0.0090 (13)	0.0103 (13)	0.0055 (13)
P	0.0165 (4)	0.0155 (4)	0.0176 (3)	0.0009 (3)	0.0048 (3)	0.0000 (3)
C20	0.0229 (15)	0.0162 (14)	0.0161 (12)	0.0019 (11)	0.0040 (10)	0.0034 (11)
C21	0.0255 (16)	0.0204 (15)	0.0214 (14)	−0.0003 (12)	0.0049 (11)	−0.0005 (12)
C22	0.0395 (19)	0.0245 (16)	0.0292 (15)	0.0036 (14)	0.0152 (13)	−0.0022 (13)
C23	0.052 (2)	0.0188 (16)	0.0213 (14)	−0.0034 (14)	0.0081 (13)	−0.0042 (12)
C24	0.0368 (18)	0.0271 (17)	0.0205 (14)	−0.0136 (14)	0.0015 (12)	0.0014 (13)
C25	0.0240 (15)	0.0244 (16)	0.0208 (14)	−0.0020 (12)	0.0041 (11)	0.0032 (12)
C26	0.0183 (14)	0.0213 (15)	0.0157 (12)	−0.0007 (11)	0.0052 (10)	−0.0016 (11)
C27	0.0269 (16)	0.0240 (16)	0.0200 (13)	−0.0029 (13)	0.0044 (11)	0.0013 (12)
C28	0.0339 (18)	0.0357 (18)	0.0226 (15)	−0.0159 (15)	0.0055 (13)	0.0011 (13)
C29	0.0201 (15)	0.049 (2)	0.0216 (14)	−0.0096 (14)	0.0047 (12)	−0.0051 (14)
C30	0.0201 (16)	0.0382 (19)	0.0271 (15)	0.0046 (14)	0.0035 (12)	−0.0060 (14)
C31	0.0221 (15)	0.0250 (16)	0.0241 (14)	0.0019 (12)	0.0049 (11)	−0.0019 (12)

Geometric parameters (Å, º)

Ni—N	2.006 (2)	C13—H13	0.9500
Ni—P	2.2719 (7)	C14—C19	1.392 (4)
Ni—Br1	2.3365 (4)	C14—C15	1.416 (4)
Ni—Br2	2.3597 (4)	C15—C16	1.385 (3)
N—C13	1.287 (3)	C15—P	1.826 (3)
N—C1	1.466 (3)	C16—C17	1.396 (4)
C1—C6	1.392 (4)	C16—H16	0.9500
C1—C2	1.399 (4)	C17—C18	1.373 (4)
C2—C3	1.398 (4)	C17—H17	0.9500
C2—C7	1.519 (4)	C18—C19	1.393 (4)
C3—C4	1.371 (4)	C18—H18	0.9500
C3—H3	0.9500	C19—H19	0.9500
C4—C5	1.380 (4)	P—C26	1.812 (3)
C4—H4	0.9500	P—C20	1.820 (3)
C5—C6	1.395 (4)	C20—C21	1.398 (4)
C5—H5	0.9500	C20—C25	1.400 (4)
C6—C10	1.522 (4)	C21—C22	1.390 (4)
C7—C9	1.527 (4)	C21—H21	0.9500
C7—C8	1.532 (4)	C22—C23	1.378 (4)
C7—H7	1.0000	C22—H22	0.9500
C8—H8A	0.9800	C23—C24	1.382 (4)
C8—H8B	0.9800	C23—H23	0.9500
C8—H8C	0.9800	C24—C25	1.389 (4)
C9—H9A	0.9800	C24—H24	0.9500
C9—H9B	0.9800	C25—H25	0.9500
C9—H9C	0.9800	C26—C27	1.391 (4)
C10—C11	1.523 (4)	C26—C31	1.405 (4)
C10—C12	1.525 (4)	C27—C28	1.387 (4)
C10—H10	1.0000	C27—H27	0.9500
C11—H11A	0.9800	C28—C29	1.373 (4)
C11—H11B	0.9800	C28—H28	0.9500
C11—H11C	0.9800	C29—C30	1.383 (4)
C12—H12A	0.9800	C29—H29	0.9500
C12—H12B	0.9800	C30—C31	1.385 (4)
C12—H12C	0.9800	C30—H30	0.9500
C13—C14	1.474 (4)	C31—H31	0.9500
N—Ni—P	91.07 (6)	N—C13—C14	127.2 (2)
N—Ni—Br1	109.57 (6)	N—C13—H13	116.4
P—Ni—Br1	112.95 (2)	C14—C13—H13	116.4
N—Ni—Br2	108.42 (6)	C19—C14—C15	119.7 (2)
P—Ni—Br2	102.63 (2)	C19—C14—C13	114.1 (2)
Br1—Ni—Br2	126.385 (18)	C15—C14—C13	126.2 (2)
C13—N—C1	115.1 (2)	C16—C15—C14	118.3 (2)
C13—N—Ni	126.04 (18)	C16—C15—P	121.3 (2)
C1—N—Ni	118.53 (16)	C14—C15—P	120.40 (19)
C6—C1—C2	122.8 (2)	C15—C16—C17	121.4 (3)
C6—C1—N	119.0 (2)	C15—C16—H16	119.3
C2—C1—N	118.2 (2)	C17—C16—H16	119.3
C3—C2—C1	117.0 (2)	C18—C17—C16	120.1 (3)
C3—C2—C7	119.2 (2)	C18—C17—H17	119.9
C1—C2—C7	123.7 (2)	C16—C17—H17	119.9
C4—C3—C2	121.5 (3)	C17—C18—C19	119.6 (3)
C4—C3—H3	119.2	C17—C18—H18	120.2
C2—C3—H3	119.2	C19—C18—H18	120.2
C3—C4—C5	120.1 (3)	C14—C19—C18	120.8 (3)
C3—C4—H4	120.0	C14—C19—H19	119.6
C5—C4—H4	120.0	C18—C19—H19	119.6
C4—C5—C6	121.1 (3)	C26—P—C20	104.41 (12)
C4—C5—H5	119.4	C26—P—C15	107.52 (12)
C6—C5—H5	119.4	C20—P—C15	105.54 (12)
C1—C6—C5	117.4 (2)	C26—P—Ni	113.89 (8)
C1—C6—C10	122.7 (2)	C20—P—Ni	121.35 (9)
C5—C6—C10	119.9 (2)	C15—P—Ni	103.19 (8)
C2—C7—C9	112.1 (2)	C21—C20—C25	119.1 (2)
C2—C7—C8	109.6 (2)	C21—C20—P	121.9 (2)
C9—C7—C8	111.5 (2)	C25—C20—P	119.1 (2)
C2—C7—H7	107.8	C22—C21—C20	120.5 (3)
C9—C7—H7	107.8	C22—C21—H21	119.8
C8—C7—H7	107.8	C20—C21—H21	119.8
C7—C8—H8A	109.5	C23—C22—C21	119.9 (3)
C7—C8—H8B	109.5	C23—C22—H22	120.0
H8A—C8—H8B	109.5	C21—C22—H22	120.0
C7—C8—H8C	109.5	C22—C23—C24	120.2 (3)
H8A—C8—H8C	109.5	C22—C23—H23	119.9
H8B—C8—H8C	109.5	C24—C23—H23	119.9
C7—C9—H9A	109.5	C23—C24—C25	120.6 (3)
C7—C9—H9B	109.5	C23—C24—H24	119.7
H9A—C9—H9B	109.5	C25—C24—H24	119.7
C7—C9—H9C	109.5	C24—C25—C20	119.7 (3)
H9A—C9—H9C	109.5	C24—C25—H25	120.2
H9B—C9—H9C	109.5	C20—C25—H25	120.2
C6—C10—C11	110.9 (2)	C27—C26—C31	119.2 (2)
C6—C10—C12	111.6 (2)	C27—C26—P	123.7 (2)
C11—C10—C12	111.4 (2)	C31—C26—P	117.0 (2)
C6—C10—H10	107.6	C28—C27—C26	119.8 (3)
C11—C10—H10	107.6	C28—C27—H27	120.1
C12—C10—H10	107.6	C26—C27—H27	120.1
C10—C11—H11A	109.5	C29—C28—C27	120.7 (3)
C10—C11—H11B	109.5	C29—C28—H28	119.7
H11A—C11—H11B	109.5	C27—C28—H28	119.7
C10—C11—H11C	109.5	C28—C29—C30	120.2 (3)
H11A—C11—H11C	109.5	C28—C29—H29	119.9
H11B—C11—H11C	109.5	C30—C29—H29	119.9
C10—C12—H12A	109.5	C29—C30—C31	120.1 (3)
C10—C12—H12B	109.5	C29—C30—H30	120.0
H12A—C12—H12B	109.5	C31—C30—H30	120.0
C10—C12—H12C	109.5	C30—C31—C26	119.9 (3)
H12A—C12—H12C	109.5	C30—C31—H31	120.0
H12B—C12—H12C	109.5	C26—C31—H31	120.0
P—Ni—N—C13	39.4 (2)	C13—C14—C19—C18	−176.1 (3)
Br1—Ni—N—C13	154.2 (2)	C17—C18—C19—C14	−2.7 (5)
Br2—Ni—N—C13	−64.3 (2)	C16—C15—P—C26	99.7 (2)
P—Ni—N—C1	−147.52 (17)	C14—C15—P—C26	−82.8 (2)
Br1—Ni—N—C1	−32.65 (18)	C16—C15—P—C20	−11.3 (3)
Br2—Ni—N—C1	108.79 (17)	C14—C15—P—C20	166.2 (2)
C13—N—C1—C6	−90.4 (3)	C16—C15—P—Ni	−139.6 (2)
Ni—N—C1—C6	95.7 (2)	C14—C15—P—Ni	37.9 (2)
C13—N—C1—C2	89.4 (3)	N—Ni—P—C26	68.87 (11)
Ni—N—C1—C2	−84.5 (3)	Br1—Ni—P—C26	−42.95 (10)
C6—C1—C2—C3	1.4 (4)	Br2—Ni—P—C26	178.01 (10)
N—C1—C2—C3	−178.4 (2)	N—Ni—P—C20	−165.08 (12)
C6—C1—C2—C7	178.7 (2)	Br1—Ni—P—C20	83.10 (10)
N—C1—C2—C7	−1.1 (4)	Br2—Ni—P—C20	−55.93 (10)
C1—C2—C3—C4	1.0 (4)	N—Ni—P—C15	−47.37 (10)
C7—C2—C3—C4	−176.4 (3)	Br1—Ni—P—C15	−159.19 (9)
C2—C3—C4—C5	−1.4 (4)	Br2—Ni—P—C15	61.78 (9)
C3—C4—C5—C6	−0.5 (4)	C26—P—C20—C21	6.9 (2)
C2—C1—C6—C5	−3.2 (4)	C15—P—C20—C21	120.1 (2)
N—C1—C6—C5	176.6 (2)	Ni—P—C20—C21	−123.4 (2)
C2—C1—C6—C10	177.7 (3)	C26—P—C20—C25	−173.1 (2)
N—C1—C6—C10	−2.5 (4)	C15—P—C20—C25	−59.9 (2)
C4—C5—C6—C1	2.7 (4)	Ni—P—C20—C25	56.6 (2)
C4—C5—C6—C10	−178.2 (3)	C25—C20—C21—C22	−0.1 (4)
C3—C2—C7—C9	−58.3 (3)	P—C20—C21—C22	179.9 (2)
C1—C2—C7—C9	124.5 (3)	C20—C21—C22—C23	1.7 (4)
C3—C2—C7—C8	66.1 (3)	C21—C22—C23—C24	−1.4 (4)
C1—C2—C7—C8	−111.0 (3)	C22—C23—C24—C25	−0.5 (4)
C1—C6—C10—C11	102.4 (3)	C23—C24—C25—C20	2.1 (4)
C5—C6—C10—C11	−76.7 (3)	C21—C20—C25—C24	−1.8 (4)
C1—C6—C10—C12	−132.8 (3)	P—C20—C25—C24	178.2 (2)
C5—C6—C10—C12	48.1 (3)	C20—P—C26—C27	103.4 (2)
C1—N—C13—C14	−178.3 (2)	C15—P—C26—C27	−8.4 (2)
Ni—N—C13—C14	−4.9 (4)	Ni—P—C26—C27	−122.1 (2)
N—C13—C14—C19	153.4 (3)	C20—P—C26—C31	−73.8 (2)
N—C13—C14—C15	−25.8 (4)	C15—P—C26—C31	174.39 (19)
C19—C14—C15—C16	−0.7 (4)	Ni—P—C26—C31	60.7 (2)
C13—C14—C15—C16	178.5 (3)	C31—C26—C27—C28	0.8 (4)
C19—C14—C15—P	−178.2 (2)	P—C26—C27—C28	−176.3 (2)
C13—C14—C15—P	0.9 (4)	C26—C27—C28—C29	2.0 (4)
C14—C15—C16—C17	−2.4 (4)	C27—C28—C29—C30	−2.6 (4)
P—C15—C16—C17	175.2 (2)	C28—C29—C30—C31	0.3 (4)
C15—C16—C17—C18	2.9 (4)	C29—C30—C31—C26	2.6 (4)
C16—C17—C18—C19	−0.3 (5)	C27—C26—C31—C30	−3.1 (4)
C15—C14—C19—C18	3.2 (4)	P—C26—C31—C30	174.2 (2)