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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101013907/sk1498sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270101013907/sk1498Isup2.hkl
Contains datablock I

CCDC reference: 175071

Comment top

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, RNCR'—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—CHNR [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)Ln][X] and [Pd(N,P)Ln][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-Ph2PC6H4CHNR)] (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(tBuNCHCHNtBu)] (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 CN 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 top

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).

Experimental top

The ligand 2,6-iPr2C6H3NCHC6H4PPh2-2, (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(CN) 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, JH—P = 5.5 Hz, NCH); 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(CN) 1611 cm-1.

Refinement top

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 Uiso = 1.2Ueq, 1.5Ueq 1.2Ueq, respectively.

Computing details top

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 top
[Figure 1] 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 top
Crystal data top
[NiBr2(C31H32NP)]F(000) = 1352
Mr = 668.08Dx = 1.515 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 10.6639 (2) ÅCell parameters from 13744 reflections
b = 14.4016 (3) Åθ = 2.9–27.5°
c = 19.7744 (4) ŵ = 3.47 mm1
β = 105.2700 (13)°T = 120 K
V = 2929.68 (10) Å3Cube, dark red
Z = 40.18 × 0.18 × 0.17 mm
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
6683 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode4970 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.057
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
ϕ and ω scans to fill the Ewald sphereh = 1313
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
k = 1718
Tmin = 0.843, Tmax = 0.947l = 2525
22746 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.036Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.083H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.0359P)2]
where P = (Fo2 + 2Fc2)/3
6683 reflections(Δ/σ)max = 0.001
329 parametersΔρmax = 0.48 e Å3
0 restraintsΔρmin = 0.70 e Å3
Crystal data top
[NiBr2(C31H32NP)]V = 2929.68 (10) Å3
Mr = 668.08Z = 4
Monoclinic, P21/nMo Kα radiation
a = 10.6639 (2) ŵ = 3.47 mm1
b = 14.4016 (3) ÅT = 120 K
c = 19.7744 (4) Å0.18 × 0.18 × 0.17 mm
β = 105.2700 (13)°
Data collection top
Enraf Nonius KappaCCD area-detector
diffractometer
6683 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995, 1997)
4970 reflections with I > 2σ(I)
Tmin = 0.843, Tmax = 0.947Rint = 0.057
22746 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.083H-atom parameters constrained
S = 1.05Δρmax = 0.48 e Å3
6683 reflectionsΔρmin = 0.70 e Å3
329 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
Ni0.37422 (3)0.89318 (2)0.238242 (16)0.01763 (9)
Br10.53546 (3)0.81495 (2)0.321789 (14)0.02692 (9)
Br20.15675 (3)0.84497 (2)0.192938 (14)0.02649 (9)
N0.3743 (2)1.02785 (15)0.26413 (10)0.0179 (5)
C10.4094 (3)1.05294 (18)0.33859 (13)0.0184 (6)
C20.3123 (3)1.05027 (19)0.37424 (13)0.0195 (6)
C30.3476 (3)1.07687 (19)0.44474 (13)0.0229 (6)
H30.28441.07500.47080.028*
C40.4715 (3)1.10560 (19)0.47717 (14)0.0242 (6)
H40.49271.12470.52480.029*
C50.5654 (3)1.10683 (19)0.44065 (13)0.0225 (6)
H50.65071.12730.46350.027*
C60.5371 (3)1.07855 (18)0.37077 (13)0.0189 (6)
C70.1718 (3)1.02452 (19)0.33988 (14)0.0224 (6)
H70.16621.00410.29080.027*
C80.0852 (3)1.1104 (2)0.33587 (15)0.0306 (7)
H8A0.08361.12900.38330.046*
H8B0.00321.09570.30840.046*
H8C0.12001.16130.31340.046*
C90.1251 (3)0.9442 (2)0.37744 (15)0.0346 (7)
H9A0.18130.89010.37820.052*
H9B0.03550.92830.35260.052*
H9C0.12860.96270.42560.052*
C100.6437 (3)1.07801 (19)0.33256 (14)0.0227 (6)
H100.61121.04130.28850.027*
C110.6720 (3)1.1761 (2)0.31171 (17)0.0365 (8)
H11A0.59391.20180.27920.055*
H11B0.74301.17430.28880.055*
H11C0.69701.21520.35370.055*
C120.7667 (3)1.0306 (2)0.37582 (16)0.0356 (8)
H12A0.82621.01980.34640.053*
H12B0.74380.97110.39340.053*
H12C0.80901.07050.41540.053*
C130.3346 (3)1.09566 (19)0.22147 (13)0.0206 (6)
H130.33411.15530.24190.025*
C140.2898 (3)1.09103 (18)0.14439 (13)0.0195 (6)
C150.3258 (2)1.02324 (18)0.10111 (13)0.0180 (6)
C160.2715 (3)1.0285 (2)0.02944 (13)0.0236 (6)
H160.29710.98500.00050.028*
C170.1800 (3)1.0965 (2)0.00018 (14)0.0295 (7)
H170.14111.09710.04890.035*
C180.1460 (3)1.1625 (2)0.04224 (15)0.0309 (7)
H180.08411.20900.02240.037*
C190.2030 (3)1.1610 (2)0.11421 (15)0.0289 (7)
H190.18241.20820.14300.035*
P0.43589 (6)0.92893 (5)0.13980 (3)0.01647 (15)
C200.4234 (3)0.84454 (18)0.06983 (13)0.0186 (6)
C210.5311 (3)0.81881 (19)0.04632 (13)0.0227 (6)
H210.61360.84580.06700.027*
C220.5183 (3)0.7540 (2)0.00718 (14)0.0299 (7)
H220.59240.73560.02210.036*
C230.3982 (3)0.7165 (2)0.03860 (14)0.0310 (7)
H230.38920.67330.07580.037*
C240.2908 (3)0.7417 (2)0.01608 (13)0.0293 (7)
H240.20820.71590.03830.035*
C250.3025 (3)0.80427 (19)0.03870 (13)0.0234 (6)
H250.22880.81970.05490.028*
C260.6004 (2)0.97306 (19)0.15681 (12)0.0183 (6)
C270.6316 (3)1.0592 (2)0.13392 (13)0.0240 (6)
H270.56461.10020.11020.029*
C280.7609 (3)1.0852 (2)0.14586 (14)0.0311 (7)
H280.78201.14480.13150.037*
C290.8587 (3)1.0255 (2)0.17816 (14)0.0303 (7)
H290.94691.04300.18430.036*
C300.8293 (3)0.9399 (2)0.20177 (14)0.0290 (7)
H300.89720.89890.22430.035*
C310.7008 (3)0.9140 (2)0.19263 (13)0.0240 (6)
H310.68070.85630.21060.029*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Ni0.01971 (19)0.01514 (18)0.01874 (17)0.00005 (14)0.00631 (13)0.00068 (14)
Br10.02717 (17)0.02666 (17)0.02424 (15)0.00301 (12)0.00202 (11)0.00561 (12)
Br20.01957 (16)0.02659 (17)0.03423 (17)0.00351 (12)0.00875 (12)0.00290 (12)
N0.0147 (11)0.0196 (12)0.0199 (11)0.0005 (9)0.0055 (9)0.0026 (10)
C10.0233 (15)0.0132 (13)0.0183 (13)0.0022 (11)0.0051 (10)0.0017 (11)
C20.0203 (14)0.0181 (14)0.0197 (13)0.0020 (11)0.0043 (10)0.0004 (11)
C30.0259 (16)0.0243 (15)0.0207 (13)0.0022 (12)0.0099 (11)0.0013 (12)
C40.0265 (16)0.0237 (16)0.0216 (14)0.0013 (12)0.0051 (12)0.0058 (12)
C50.0210 (15)0.0209 (15)0.0242 (14)0.0020 (12)0.0038 (11)0.0046 (12)
C60.0217 (15)0.0125 (13)0.0231 (13)0.0006 (11)0.0069 (11)0.0014 (11)
C70.0217 (15)0.0252 (16)0.0223 (13)0.0017 (12)0.0093 (11)0.0019 (12)
C80.0218 (16)0.0329 (18)0.0357 (16)0.0031 (13)0.0052 (13)0.0021 (14)
C90.0328 (18)0.0347 (19)0.0368 (17)0.0093 (15)0.0101 (14)0.0030 (15)
C100.0200 (15)0.0251 (16)0.0245 (14)0.0032 (12)0.0083 (11)0.0081 (12)
C110.0383 (19)0.0327 (19)0.0438 (19)0.0060 (15)0.0202 (15)0.0011 (15)
C120.0235 (17)0.043 (2)0.0416 (18)0.0010 (15)0.0117 (14)0.0078 (16)
C130.0210 (15)0.0161 (14)0.0262 (14)0.0000 (11)0.0088 (11)0.0021 (12)
C140.0193 (14)0.0172 (14)0.0221 (13)0.0003 (11)0.0058 (11)0.0011 (11)
C150.0160 (14)0.0168 (14)0.0221 (13)0.0003 (11)0.0063 (10)0.0024 (11)
C160.0264 (16)0.0237 (16)0.0217 (14)0.0024 (12)0.0079 (11)0.0010 (12)
C170.0315 (17)0.0340 (18)0.0212 (14)0.0063 (14)0.0037 (12)0.0076 (13)
C180.0300 (17)0.0275 (17)0.0350 (17)0.0119 (14)0.0083 (13)0.0106 (14)
C190.0330 (18)0.0231 (16)0.0315 (16)0.0090 (13)0.0103 (13)0.0055 (13)
P0.0165 (4)0.0155 (4)0.0176 (3)0.0009 (3)0.0048 (3)0.0000 (3)
C200.0229 (15)0.0162 (14)0.0161 (12)0.0019 (11)0.0040 (10)0.0034 (11)
C210.0255 (16)0.0204 (15)0.0214 (14)0.0003 (12)0.0049 (11)0.0005 (12)
C220.0395 (19)0.0245 (16)0.0292 (15)0.0036 (14)0.0152 (13)0.0022 (13)
C230.052 (2)0.0188 (16)0.0213 (14)0.0034 (14)0.0081 (13)0.0042 (12)
C240.0368 (18)0.0271 (17)0.0205 (14)0.0136 (14)0.0015 (12)0.0014 (13)
C250.0240 (15)0.0244 (16)0.0208 (14)0.0020 (12)0.0041 (11)0.0032 (12)
C260.0183 (14)0.0213 (15)0.0157 (12)0.0007 (11)0.0052 (10)0.0016 (11)
C270.0269 (16)0.0240 (16)0.0200 (13)0.0029 (13)0.0044 (11)0.0013 (12)
C280.0339 (18)0.0357 (18)0.0226 (15)0.0159 (15)0.0055 (13)0.0011 (13)
C290.0201 (15)0.049 (2)0.0216 (14)0.0096 (14)0.0047 (12)0.0051 (14)
C300.0201 (16)0.0382 (19)0.0271 (15)0.0046 (14)0.0035 (12)0.0060 (14)
C310.0221 (15)0.0250 (16)0.0241 (14)0.0019 (12)0.0049 (11)0.0019 (12)
Geometric parameters (Å, º) top
Ni—N2.006 (2)C13—H130.9500
Ni—P2.2719 (7)C14—C191.392 (4)
Ni—Br12.3365 (4)C14—C151.416 (4)
Ni—Br22.3597 (4)C15—C161.385 (3)
N—C131.287 (3)C15—P1.826 (3)
N—C11.466 (3)C16—C171.396 (4)
C1—C61.392 (4)C16—H160.9500
C1—C21.399 (4)C17—C181.373 (4)
C2—C31.398 (4)C17—H170.9500
C2—C71.519 (4)C18—C191.393 (4)
C3—C41.371 (4)C18—H180.9500
C3—H30.9500C19—H190.9500
C4—C51.380 (4)P—C261.812 (3)
C4—H40.9500P—C201.820 (3)
C5—C61.395 (4)C20—C211.398 (4)
C5—H50.9500C20—C251.400 (4)
C6—C101.522 (4)C21—C221.390 (4)
C7—C91.527 (4)C21—H210.9500
C7—C81.532 (4)C22—C231.378 (4)
C7—H71.0000C22—H220.9500
C8—H8A0.9800C23—C241.382 (4)
C8—H8B0.9800C23—H230.9500
C8—H8C0.9800C24—C251.389 (4)
C9—H9A0.9800C24—H240.9500
C9—H9B0.9800C25—H250.9500
C9—H9C0.9800C26—C271.391 (4)
C10—C111.523 (4)C26—C311.405 (4)
C10—C121.525 (4)C27—C281.387 (4)
C10—H101.0000C27—H270.9500
C11—H11A0.9800C28—C291.373 (4)
C11—H11B0.9800C28—H280.9500
C11—H11C0.9800C29—C301.383 (4)
C12—H12A0.9800C29—H290.9500
C12—H12B0.9800C30—C311.385 (4)
C12—H12C0.9800C30—H300.9500
C13—C141.474 (4)C31—H310.9500
N—Ni—P91.07 (6)N—C13—C14127.2 (2)
N—Ni—Br1109.57 (6)N—C13—H13116.4
P—Ni—Br1112.95 (2)C14—C13—H13116.4
N—Ni—Br2108.42 (6)C19—C14—C15119.7 (2)
P—Ni—Br2102.63 (2)C19—C14—C13114.1 (2)
Br1—Ni—Br2126.385 (18)C15—C14—C13126.2 (2)
C13—N—C1115.1 (2)C16—C15—C14118.3 (2)
C13—N—Ni126.04 (18)C16—C15—P121.3 (2)
C1—N—Ni118.53 (16)C14—C15—P120.40 (19)
C6—C1—C2122.8 (2)C15—C16—C17121.4 (3)
C6—C1—N119.0 (2)C15—C16—H16119.3
C2—C1—N118.2 (2)C17—C16—H16119.3
C3—C2—C1117.0 (2)C18—C17—C16120.1 (3)
C3—C2—C7119.2 (2)C18—C17—H17119.9
C1—C2—C7123.7 (2)C16—C17—H17119.9
C4—C3—C2121.5 (3)C17—C18—C19119.6 (3)
C4—C3—H3119.2C17—C18—H18120.2
C2—C3—H3119.2C19—C18—H18120.2
C3—C4—C5120.1 (3)C14—C19—C18120.8 (3)
C3—C4—H4120.0C14—C19—H19119.6
C5—C4—H4120.0C18—C19—H19119.6
C4—C5—C6121.1 (3)C26—P—C20104.41 (12)
C4—C5—H5119.4C26—P—C15107.52 (12)
C6—C5—H5119.4C20—P—C15105.54 (12)
C1—C6—C5117.4 (2)C26—P—Ni113.89 (8)
C1—C6—C10122.7 (2)C20—P—Ni121.35 (9)
C5—C6—C10119.9 (2)C15—P—Ni103.19 (8)
C2—C7—C9112.1 (2)C21—C20—C25119.1 (2)
C2—C7—C8109.6 (2)C21—C20—P121.9 (2)
C9—C7—C8111.5 (2)C25—C20—P119.1 (2)
C2—C7—H7107.8C22—C21—C20120.5 (3)
C9—C7—H7107.8C22—C21—H21119.8
C8—C7—H7107.8C20—C21—H21119.8
C7—C8—H8A109.5C23—C22—C21119.9 (3)
C7—C8—H8B109.5C23—C22—H22120.0
H8A—C8—H8B109.5C21—C22—H22120.0
C7—C8—H8C109.5C22—C23—C24120.2 (3)
H8A—C8—H8C109.5C22—C23—H23119.9
H8B—C8—H8C109.5C24—C23—H23119.9
C7—C9—H9A109.5C23—C24—C25120.6 (3)
C7—C9—H9B109.5C23—C24—H24119.7
H9A—C9—H9B109.5C25—C24—H24119.7
C7—C9—H9C109.5C24—C25—C20119.7 (3)
H9A—C9—H9C109.5C24—C25—H25120.2
H9B—C9—H9C109.5C20—C25—H25120.2
C6—C10—C11110.9 (2)C27—C26—C31119.2 (2)
C6—C10—C12111.6 (2)C27—C26—P123.7 (2)
C11—C10—C12111.4 (2)C31—C26—P117.0 (2)
C6—C10—H10107.6C28—C27—C26119.8 (3)
C11—C10—H10107.6C28—C27—H27120.1
C12—C10—H10107.6C26—C27—H27120.1
C10—C11—H11A109.5C29—C28—C27120.7 (3)
C10—C11—H11B109.5C29—C28—H28119.7
H11A—C11—H11B109.5C27—C28—H28119.7
C10—C11—H11C109.5C28—C29—C30120.2 (3)
H11A—C11—H11C109.5C28—C29—H29119.9
H11B—C11—H11C109.5C30—C29—H29119.9
C10—C12—H12A109.5C29—C30—C31120.1 (3)
C10—C12—H12B109.5C29—C30—H30120.0
H12A—C12—H12B109.5C31—C30—H30120.0
C10—C12—H12C109.5C30—C31—C26119.9 (3)
H12A—C12—H12C109.5C30—C31—H31120.0
H12B—C12—H12C109.5C26—C31—H31120.0
P—Ni—N—C1339.4 (2)C13—C14—C19—C18176.1 (3)
Br1—Ni—N—C13154.2 (2)C17—C18—C19—C142.7 (5)
Br2—Ni—N—C1364.3 (2)C16—C15—P—C2699.7 (2)
P—Ni—N—C1147.52 (17)C14—C15—P—C2682.8 (2)
Br1—Ni—N—C132.65 (18)C16—C15—P—C2011.3 (3)
Br2—Ni—N—C1108.79 (17)C14—C15—P—C20166.2 (2)
C13—N—C1—C690.4 (3)C16—C15—P—Ni139.6 (2)
Ni—N—C1—C695.7 (2)C14—C15—P—Ni37.9 (2)
C13—N—C1—C289.4 (3)N—Ni—P—C2668.87 (11)
Ni—N—C1—C284.5 (3)Br1—Ni—P—C2642.95 (10)
C6—C1—C2—C31.4 (4)Br2—Ni—P—C26178.01 (10)
N—C1—C2—C3178.4 (2)N—Ni—P—C20165.08 (12)
C6—C1—C2—C7178.7 (2)Br1—Ni—P—C2083.10 (10)
N—C1—C2—C71.1 (4)Br2—Ni—P—C2055.93 (10)
C1—C2—C3—C41.0 (4)N—Ni—P—C1547.37 (10)
C7—C2—C3—C4176.4 (3)Br1—Ni—P—C15159.19 (9)
C2—C3—C4—C51.4 (4)Br2—Ni—P—C1561.78 (9)
C3—C4—C5—C60.5 (4)C26—P—C20—C216.9 (2)
C2—C1—C6—C53.2 (4)C15—P—C20—C21120.1 (2)
N—C1—C6—C5176.6 (2)Ni—P—C20—C21123.4 (2)
C2—C1—C6—C10177.7 (3)C26—P—C20—C25173.1 (2)
N—C1—C6—C102.5 (4)C15—P—C20—C2559.9 (2)
C4—C5—C6—C12.7 (4)Ni—P—C20—C2556.6 (2)
C4—C5—C6—C10178.2 (3)C25—C20—C21—C220.1 (4)
C3—C2—C7—C958.3 (3)P—C20—C21—C22179.9 (2)
C1—C2—C7—C9124.5 (3)C20—C21—C22—C231.7 (4)
C3—C2—C7—C866.1 (3)C21—C22—C23—C241.4 (4)
C1—C2—C7—C8111.0 (3)C22—C23—C24—C250.5 (4)
C1—C6—C10—C11102.4 (3)C23—C24—C25—C202.1 (4)
C5—C6—C10—C1176.7 (3)C21—C20—C25—C241.8 (4)
C1—C6—C10—C12132.8 (3)P—C20—C25—C24178.2 (2)
C5—C6—C10—C1248.1 (3)C20—P—C26—C27103.4 (2)
C1—N—C13—C14178.3 (2)C15—P—C26—C278.4 (2)
Ni—N—C13—C144.9 (4)Ni—P—C26—C27122.1 (2)
N—C13—C14—C19153.4 (3)C20—P—C26—C3173.8 (2)
N—C13—C14—C1525.8 (4)C15—P—C26—C31174.39 (19)
C19—C14—C15—C160.7 (4)Ni—P—C26—C3160.7 (2)
C13—C14—C15—C16178.5 (3)C31—C26—C27—C280.8 (4)
C19—C14—C15—P178.2 (2)P—C26—C27—C28176.3 (2)
C13—C14—C15—P0.9 (4)C26—C27—C28—C292.0 (4)
C14—C15—C16—C172.4 (4)C27—C28—C29—C302.6 (4)
P—C15—C16—C17175.2 (2)C28—C29—C30—C310.3 (4)
C15—C16—C17—C182.9 (4)C29—C30—C31—C262.6 (4)
C16—C17—C18—C190.3 (5)C27—C26—C31—C303.1 (4)
C15—C14—C19—C183.2 (4)P—C26—C31—C30174.2 (2)

Experimental details

Crystal data
Chemical formula[NiBr2(C31H32NP)]
Mr668.08
Crystal system, space groupMonoclinic, P21/n
Temperature (K)120
a, b, c (Å)10.6639 (2), 14.4016 (3), 19.7744 (4)
β (°) 105.2700 (13)
V3)2929.68 (10)
Z4
Radiation typeMo Kα
µ (mm1)3.47
Crystal size (mm)0.18 × 0.18 × 0.17
Data collection
DiffractometerEnraf Nonius KappaCCD area-detector
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995, 1997)
Tmin, Tmax0.843, 0.947
No. of measured, independent and
observed [I > 2σ(I)] reflections
22746, 6683, 4970
Rint0.057
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.083, 1.05
No. of reflections6683
No. of parameters329
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.70

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Bond lengths and angles involving Ni (Å, °) for compounds (I)–(VI) top
(I)(II)(III)(IV)(V)(VI)-1(VI)-2
Ni—X2.3365 (4)2.203 (2)2.167 (2)1.975 (3)1.875 (6)1.877 (3)1.881 (3)
Ni—Y2.3597 (4)2.211 (2)1.895 (6)2.144 (2)2.148 (3)2.1702 (13)2.1540 (14)
Ni—P2.2719 (7)2.274 (3)2.173 (2)2.1378 (9)2.142 (2)2.1480 (13)2.1374 (14)
Ni—N2.006 (2)2.000 (3)1.891 (6)1.875 (3)1.900 (7)1.860 (3)1.848 (3)
X—Ni—Y126.385 (18)128.15 (6)89.03 (17)91.98 (9)90.4 (2)91.58 (9)91.69 (9)
X—Ni—P112.95 (2)118.89 (7)163.11 (9)176.18 (11)168.3 (2)173.65 (9)175.23 (9)
X—Ni—N109.57 (6)113.22 (15)87.94 (17)84.72 (12)86.3 (3)83.67 (14)83.94 (12)
Y—Ni—P102.63 (2)98.00 (12)90.57 (17)91.77 (8)92.26 (11)89.90 (5)89.21 (5)
Y—Ni—N108.42 (6)103.35 (9)176.5 (2)171.78 (4)175.1 (2)174.40 (11)174.87 (11)
P—Ni—N91.07 (6)86.71 (9)92.84 (17)91.47 (10)91.7 (2)95.14 (12)94.91 (10)
Notes: for (I) and (II), X = Y = Br or Cl, and X = Br1 or Cl1, respectively, such that Ni—X < Ni—Y. For (III)–(VI), with square-planar nickel, X represents the atom trans to the iminophosphine P atom [S for (III) and O for (IV)–(VI)]. Likewise, Y now represents the atom trans to the iminophosphine N atom [N for (III) and Cl for the rest]. The suffices -1 and -2 distinguish between the two molecules in the asymmetric unit of (VI). The values for (II)–(VI) are calculated using PLATON (Spek, 1990) from CIF data extracted from the CSD; see text for CSD codes and full references.
Puckering parameters and selected angles between planes for (I)–(VI). Puckering amplitudes (Amp) are given in Å and the θ and ϕ angles and also the interplanar angles IP1 and IP2 are given in °. top
(I)(II)(III)(IV)(V)(VI)-1(VI)-2
Amp0.724 (2)0.832 (2)0.425 (4)0.509 (2)0.446 (5)0.163 (3)0.236 (2)
θ61.9 (2)62.8 (1)58.5 (8)59.5 (3)57.6 (9)53.6 (14)57.9 (10)
ϕ26.3 (2)24.76 (19)24.6 (9)30.8 (4)11.9 (12)49.0 (15)45.1 (10)
IP124.52 (12)25.50 (11)10.1 (3)14.69 (17)10.9 (4)4.33 (19)6.14 (19)
IP214.3 (2)28.76 (15)19.7 (3)3.43 (13)7.19 (14)
Notes: compound designations are as for Table 1. For (V), the absolute configuration of the ring has been inverted and θ and ϕ adjusted accordingly for conformity with the other entries. IP1 is the acute angle between the least-squares planes of the six-membered chelate ring and the benzene ring of the iminophosphine ligand [e.g. C14–C19 for (I)] attached to it. IP2 is likewise the acute angle between the least-squares planes of the five-membered X,N- and six-membered N,P-chelate rings of (III)–(VI). In all cases, the values were obtained using PLATON (Spek, 1990).
 

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