Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680201509X/wn6116sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680201509X/wn6116IIsup2.hkl |
CCDC reference: 197455
A solution of the boronic ester complex (I) (50 mg) was prepared with chlorobenzene (3 ml) and pentane was diffused into it at room temperature. Crystallization was very slow, but after 72 h, orange crystals of the title compound formed. Attempted recrystallizations of the title compound from CH2Cl2/hexane or THF/hexane had similar outcomes. The NMR data are analogous to those of the iodo analogue [NiI(Ph)(dcpe)] (Bennett et al., 1985). 1H NMR (300 MHz, CD2Cl2, p.p.m.): δ 1.15–1.95 (m, 42H, dcpe), 2.04–2.18 (m, 4H, dcpe), 2.34–2.46 (m, 2H, dcpe), 6.77 (t, 1H, J = 7.2 Hz, p-Ph), 6.95 (t, 2H, J = 7.2 Hz, m-Ph), 7.45 (br t, 2H, J = 6.0 Hz, o-Ph); 13C NMR (75.4 MHz, CD2Cl2, p.p.m.): δ 19.24 (dd, J = 19.9, 11.7 Hz, PCH2), 24.90 (t, J = 23.1 Hz, PCH2), 26.17–30.68 (m, CH2), 34.50 (d, J = 18.7 Hz, PCH), 34.75 (br d, J = 25.3 Hz, PCH), 121.88 (s, p-CH), 126.04 (d, J = 6.0 Hz, o-CH), 137.68 (s, m-CH), 159.10 (dd, J = 85.7, 37.5, Ni—C); 31P{1H} NMR (80.96 MHz, CD2Cl2, p.p.m.): δ 63.3 (d), 67.6 (d, JPP = 19.5 Hz)
H atoms were included at calculated positions riding on the attached C atom and individual isotropic displacement parameters were refined.
Data collection: COLLECT (Nonius, 1997); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Watkin et al., 2001) and maXus (Mackay et al., 1999); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS and maXus.
Fig. 1. The molecular structure of the title compound, with the atom-labelling scheme. Dispacement ellipsoids are drawn at the 50% probability level and H atoms have been omitted for clarity. |
[NiBr(C6H5)(C26H48P2)]·C6H5Cl | F(000) = 1584 |
Mr = 750.89 | Dx = 1.280 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8308 (1) Å | Cell parameters from 89742 reflections |
b = 22.7790 (3) Å | θ = 2.9–27.5° |
c = 14.5238 (2) Å | µ = 1.77 mm−1 |
β = 107.4072 (5)° | T = 200 K |
V = 3734.82 (8) Å3 | Prism, yellow |
Z = 4 | 0.20 × 0.16 × 0.15 mm |
Nonius KappaCCD diffractometer | 4771 reflections with I > 3σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.044 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.9° |
Absorption correction: integration (Coppens, 1970) | h = −15→15 |
Tmin = 0.662, Tmax = 0.808 | k = −29→29 |
94198 measured reflections | l = −18→18 |
8553 independent reflections |
Refinement on F | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.030 | Only H-atom displacement parameters refined |
wR(F2) = 0.031 | Chebychev polynomial with 4 parameters 0.522, -.637, 0.215, -.339 (Carruthers & Watkin , 1979) |
S = 1.05 | (Δ/σ)max = 0.001 |
4771 reflections | Δρmax = 0.56 e Å−3 |
446 parameters | Δρmin = −0.51 e Å−3 |
Primary atom site location: structure-invariant direct methods |
[NiBr(C6H5)(C26H48P2)]·C6H5Cl | V = 3734.82 (8) Å3 |
Mr = 750.89 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.8308 (1) Å | µ = 1.77 mm−1 |
b = 22.7790 (3) Å | T = 200 K |
c = 14.5238 (2) Å | 0.20 × 0.16 × 0.15 mm |
β = 107.4072 (5)° |
Nonius KappaCCD diffractometer | 8553 independent reflections |
Absorption correction: integration (Coppens, 1970) | 4771 reflections with I > 3σ(I) |
Tmin = 0.662, Tmax = 0.808 | Rint = 0.044 |
94198 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 446 parameters |
wR(F2) = 0.031 | Only H-atom displacement parameters refined |
S = 1.05 | Δρmax = 0.56 e Å−3 |
4771 reflections | Δρmin = −0.51 e Å−3 |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.46259 (3) | 0.280369 (14) | 0.76672 (2) | 0.0320 | |
Br1 | 0.50019 (3) | 0.237201 (14) | 0.91905 (2) | 0.0479 | |
Cl1 | 0.12559 (17) | 0.45200 (6) | 0.91951 (11) | 0.1250 | |
P1 | 0.43070 (6) | 0.19424 (3) | 0.69151 (5) | 0.0341 | |
P2 | 0.41007 (6) | 0.32327 (3) | 0.62946 (5) | 0.0331 | |
C1 | 0.5164 (2) | 0.35707 (11) | 0.82877 (19) | 0.0346 | |
C2 | 0.6396 (3) | 0.36330 (13) | 0.8622 (2) | 0.0464 | |
C3 | 0.6881 (3) | 0.41487 (14) | 0.9088 (2) | 0.0522 | |
C4 | 0.6166 (3) | 0.45927 (14) | 0.9227 (2) | 0.0579 | |
C5 | 0.4953 (3) | 0.45158 (14) | 0.8913 (2) | 0.0543 | |
C6 | 0.4465 (3) | 0.39970 (13) | 0.8444 (2) | 0.0462 | |
C7 | 0.4077 (3) | 0.20758 (12) | 0.5624 (2) | 0.0415 | |
C8 | 0.3512 (2) | 0.26822 (12) | 0.5332 (2) | 0.0384 | |
C9 | 0.5612 (2) | 0.14528 (11) | 0.7269 (2) | 0.0387 | |
C10 | 0.6748 (2) | 0.17813 (13) | 0.7289 (2) | 0.0450 | |
C11 | 0.7839 (2) | 0.13823 (14) | 0.7623 (3) | 0.0507 | |
C12 | 0.7689 (3) | 0.08257 (15) | 0.7015 (3) | 0.0601 | |
C13 | 0.6565 (3) | 0.05017 (14) | 0.7002 (3) | 0.0615 | |
C14 | 0.5472 (3) | 0.08941 (13) | 0.6649 (3) | 0.0517 | |
C15 | 0.3056 (2) | 0.14549 (12) | 0.6914 (2) | 0.0391 | |
C16 | 0.3216 (3) | 0.11250 (14) | 0.7864 (2) | 0.0502 | |
C17 | 0.2187 (3) | 0.06967 (15) | 0.7773 (3) | 0.0592 | |
C18 | 0.1001 (3) | 0.10106 (16) | 0.7466 (3) | 0.0616 | |
C19 | 0.0837 (3) | 0.13651 (16) | 0.6551 (3) | 0.0578 | |
C20 | 0.1872 (2) | 0.17861 (13) | 0.6627 (2) | 0.0455 | |
C21 | 0.2859 (2) | 0.37508 (12) | 0.6137 (2) | 0.0369 | |
C22 | 0.1879 (2) | 0.34906 (13) | 0.6516 (2) | 0.0427 | |
C23 | 0.0915 (3) | 0.39504 (14) | 0.6456 (2) | 0.0512 | |
C24 | 0.0406 (3) | 0.41700 (14) | 0.5431 (2) | 0.0511 | |
C25 | 0.1357 (3) | 0.44119 (13) | 0.5029 (2) | 0.0461 | |
C26 | 0.2343 (3) | 0.39626 (12) | 0.5102 (2) | 0.0414 | |
C27 | 0.5197 (2) | 0.36377 (12) | 0.5862 (2) | 0.0385 | |
C28 | 0.5440 (3) | 0.42697 (12) | 0.6240 (2) | 0.0445 | |
C29 | 0.6324 (3) | 0.45680 (14) | 0.5813 (3) | 0.0547 | |
C30 | 0.7479 (3) | 0.42215 (15) | 0.6046 (3) | 0.0642 | |
C31 | 0.7253 (3) | 0.35961 (15) | 0.5663 (3) | 0.0619 | |
C32 | 0.6350 (2) | 0.32872 (13) | 0.6060 (2) | 0.0453 | |
C33 | 0.0998 (4) | 0.37829 (18) | 0.8979 (3) | 0.0677 | |
C34 | 0.1933 (4) | 0.3385 (2) | 0.9245 (3) | 0.0744 | |
C35 | 0.1682 (4) | 0.2797 (2) | 0.9050 (3) | 0.0761 | |
C36 | 0.0554 (5) | 0.2615 (2) | 0.8595 (3) | 0.0834 | |
C37 | −0.0367 (4) | 0.2994 (2) | 0.8329 (3) | 0.0834 | |
C38 | −0.0136 (4) | 0.3598 (2) | 0.8543 (3) | 0.0730 | |
H21 | 0.6920 (3) | 0.33094 (13) | 0.8523 (2) | 0.049 (9)* | |
H31 | 0.7761 (3) | 0.41972 (14) | 0.9318 (2) | 0.067 (11)* | |
H41 | 0.6521 (3) | 0.49642 (14) | 0.9555 (2) | 0.06 (1)* | |
H51 | 0.4420 (3) | 0.48313 (14) | 0.9023 (2) | 0.067 (11)* | |
H61 | 0.3586 (3) | 0.39431 (13) | 0.8217 (2) | 0.068 (11)* | |
H71 | 0.4859 (3) | 0.20609 (12) | 0.5492 (2) | 0.035 (7)* | |
H72 | 0.3544 (3) | 0.17652 (12) | 0.5239 (2) | 0.044 (8)* | |
H81 | 0.3687 (2) | 0.28158 (12) | 0.4734 (2) | 0.034 (7)* | |
H82 | 0.2635 (2) | 0.26493 (12) | 0.5203 (2) | 0.043 (8)* | |
H91 | 0.5694 (2) | 0.13146 (11) | 0.7940 (2) | 0.045 (8)* | |
H101 | 0.6848 (2) | 0.21262 (13) | 0.7732 (2) | 0.053 (9)* | |
H102 | 0.6669 (2) | 0.19213 (13) | 0.6620 (2) | 0.051 (9)* | |
H111 | 0.7950 (2) | 0.12656 (14) | 0.8308 (3) | 0.06 (1)* | |
H112 | 0.8553 (2) | 0.16017 (14) | 0.7580 (3) | 0.075 (12)* | |
H121 | 0.8390 (3) | 0.05629 (15) | 0.7273 (3) | 0.074 (11)* | |
H122 | 0.7628 (3) | 0.09403 (15) | 0.6337 (3) | 0.072 (12)* | |
H131 | 0.6639 (3) | 0.03752 (14) | 0.7677 (3) | 0.06 (1)* | |
H132 | 0.6467 (3) | 0.01483 (14) | 0.6577 (3) | 0.079 (12)* | |
H141 | 0.4750 (3) | 0.06755 (13) | 0.6677 (3) | 0.069 (11)* | |
H142 | 0.5380 (3) | 0.10126 (13) | 0.5967 (3) | 0.063 (11)* | |
H151 | 0.3030 (2) | 0.11455 (12) | 0.6419 (2) | 0.055 (9)* | |
H161 | 0.3214 (3) | 0.14192 (14) | 0.8375 (2) | 0.06 (1)* | |
H162 | 0.3988 (3) | 0.09101 (14) | 0.8049 (2) | 0.054 (9)* | |
H171 | 0.2293 (3) | 0.04915 (15) | 0.8402 (3) | 0.074 (12)* | |
H172 | 0.2194 (3) | 0.04017 (15) | 0.7265 (3) | 0.06 (1)* | |
H181 | 0.0974 (3) | 0.12853 (16) | 0.7996 (3) | 0.071 (12)* | |
H182 | 0.0345 (3) | 0.07179 (16) | 0.7361 (3) | 0.075 (12)* | |
H191 | 0.0086 (3) | 0.15959 (16) | 0.6410 (3) | 0.074 (11)* | |
H192 | 0.0786 (3) | 0.10850 (16) | 0.6010 (3) | 0.082 (13)* | |
H201 | 0.1893 (2) | 0.20875 (13) | 0.7133 (2) | 0.044 (8)* | |
H202 | 0.1761 (2) | 0.19851 (13) | 0.5993 (2) | 0.044 (8)* | |
H211 | 0.3181 (2) | 0.41070 (12) | 0.6531 (2) | 0.034 (7)* | |
H221 | 0.2232 (2) | 0.33592 (13) | 0.7199 (2) | 0.055 (9)* | |
H222 | 0.1517 (2) | 0.31463 (13) | 0.6106 (2) | 0.039 (8)* | |
H231 | 0.1277 (3) | 0.42907 (14) | 0.6876 (2) | 0.06 (1)* | |
H232 | 0.0270 (3) | 0.37772 (14) | 0.6684 (2) | 0.06 (1)* | |
H241 | −0.0198 (3) | 0.44815 (14) | 0.5406 (2) | 0.054 (9)* | |
H242 | 0.0019 (3) | 0.38304 (14) | 0.5020 (2) | 0.046 (8)* | |
H251 | 0.1709 (3) | 0.47673 (13) | 0.5412 (2) | 0.040 (8)* | |
H252 | 0.0993 (3) | 0.45245 (13) | 0.4338 (2) | 0.051 (9)* | |
H261 | 0.2986 (3) | 0.41464 (12) | 0.4883 (2) | 0.034 (7)* | |
H262 | 0.2007 (3) | 0.36189 (12) | 0.4681 (2) | 0.048 (9)* | |
H271 | 0.4840 (2) | 0.36861 (12) | 0.5150 (2) | 0.043 (8)* | |
H281 | 0.5783 (3) | 0.42575 (12) | 0.6958 (2) | 0.051 (9)* | |
H282 | 0.4682 (3) | 0.44964 (12) | 0.6064 (2) | 0.051 (9)* | |
H291 | 0.6494 (3) | 0.49741 (14) | 0.6081 (3) | 0.051 (9)* | |
H292 | 0.5970 (3) | 0.45887 (14) | 0.5097 (3) | 0.072 (12)* | |
H301 | 0.7834 (3) | 0.42029 (15) | 0.6763 (3) | 0.073 (12)* | |
H302 | 0.8043 (3) | 0.44215 (15) | 0.5755 (3) | 0.086 (13)* | |
H311 | 0.8014 (3) | 0.33716 (15) | 0.5842 (3) | 0.07 (1)* | |
H312 | 0.6922 (3) | 0.36139 (15) | 0.4944 (3) | 0.063 (11)* | |
H321 | 0.6704 (2) | 0.32440 (13) | 0.6773 (2) | 0.049 (9)* | |
H322 | 0.6168 (2) | 0.28901 (13) | 0.5758 (2) | 0.033 (7)* | |
H341 | 0.2755 (4) | 0.3525 (2) | 0.9579 (3) | 0.068 (11)* | |
H351 | 0.2329 (4) | 0.2498 (2) | 0.9240 (3) | 0.100 (15)* | |
H361 | 0.0404 (5) | 0.2188 (2) | 0.8444 (3) | 0.19 (3)* | |
H371 | −0.1188 (4) | 0.2854 (2) | 0.7991 (3) | 0.070 (11)* | |
H381 | −0.0792 (4) | 0.3893 (2) | 0.8380 (3) | 0.127 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.02780 (15) | 0.02679 (16) | 0.03603 (19) | 0.00113 (13) | 0.00120 (13) | −0.00099 (13) |
Br1 | 0.05188 (17) | 0.03917 (15) | 0.04293 (16) | −0.00306 (13) | −0.00057 (13) | 0.00557 (13) |
Cl1 | 0.1838 (16) | 0.0630 (7) | 0.104 (1) | −0.0126 (8) | 0.006 (1) | 0.0053 (7) |
P1 | 0.0284 (3) | 0.0271 (3) | 0.0415 (4) | 0.0008 (3) | 0.0026 (3) | −0.0011 (3) |
P2 | 0.0282 (3) | 0.0278 (3) | 0.0384 (4) | 0.0001 (2) | 0.0025 (3) | −0.0001 (3) |
C1 | 0.0351 (13) | 0.0326 (14) | 0.0308 (13) | −0.006 (1) | 0.0015 (11) | 0.008 (1) |
C2 | 0.0410 (15) | 0.0433 (16) | 0.0490 (18) | −0.0022 (13) | 0.0042 (13) | −0.0030 (13) |
C3 | 0.0519 (19) | 0.0463 (18) | 0.0521 (19) | −0.0141 (15) | 0.0059 (15) | −0.0012 (14) |
C4 | 0.075 (2) | 0.0376 (17) | 0.055 (2) | −0.0140 (16) | 0.0095 (17) | −0.0064 (14) |
C5 | 0.068 (2) | 0.0407 (17) | 0.0506 (19) | 0.0060 (15) | 0.0117 (16) | −0.0066 (14) |
C6 | 0.0467 (17) | 0.0475 (17) | 0.0392 (17) | −0.0064 (13) | 0.0049 (13) | −0.0043 (13) |
C7 | 0.0368 (14) | 0.0338 (15) | 0.0482 (17) | −0.0002 (11) | 0.0042 (12) | −0.0055 (12) |
C8 | 0.0345 (13) | 0.0385 (15) | 0.0366 (14) | 0.0004 (11) | 0.0024 (11) | −0.0004 (12) |
C9 | 0.0292 (13) | 0.0312 (13) | 0.0510 (18) | 0.002 (1) | 0.0048 (12) | 0.0016 (12) |
C10 | 0.0332 (14) | 0.0386 (15) | 0.060 (2) | −0.0007 (11) | 0.0089 (13) | −0.0000 (14) |
C11 | 0.0286 (14) | 0.0568 (19) | 0.065 (2) | 0.0037 (13) | 0.0110 (14) | 0.0009 (16) |
C12 | 0.0402 (17) | 0.0534 (19) | 0.089 (3) | 0.0105 (14) | 0.0226 (17) | −0.0006 (18) |
C13 | 0.0468 (18) | 0.0384 (17) | 0.098 (3) | 0.0089 (14) | 0.0205 (18) | −0.0063 (17) |
C14 | 0.0379 (16) | 0.0334 (15) | 0.079 (3) | 0.0036 (12) | 0.0106 (15) | −0.0091 (15) |
C15 | 0.0285 (13) | 0.0322 (14) | 0.0527 (18) | −0.001 (1) | 0.0064 (12) | −0.0030 (12) |
C16 | 0.0347 (15) | 0.0439 (17) | 0.067 (2) | −0.0034 (12) | 0.0070 (14) | 0.0118 (15) |
C17 | 0.0438 (17) | 0.0456 (18) | 0.084 (3) | −0.0072 (14) | 0.0133 (17) | 0.0086 (18) |
C18 | 0.0432 (18) | 0.058 (2) | 0.086 (3) | −0.0068 (15) | 0.0234 (18) | 0.0021 (19) |
C19 | 0.0299 (15) | 0.062 (2) | 0.076 (2) | −0.0014 (14) | 0.0079 (15) | −0.0051 (18) |
C20 | 0.0321 (14) | 0.0435 (16) | 0.0566 (19) | 0.0038 (12) | 0.0069 (13) | 0.0039 (14) |
C21 | 0.0314 (13) | 0.0306 (13) | 0.0438 (16) | 0.001 (1) | 0.0038 (11) | −0.0015 (11) |
C22 | 0.0367 (15) | 0.0392 (15) | 0.0505 (18) | 0.0016 (12) | 0.0103 (13) | 0.0038 (13) |
C23 | 0.0433 (17) | 0.0494 (18) | 0.063 (2) | 0.0057 (14) | 0.0195 (15) | −0.0009 (15) |
C24 | 0.0405 (16) | 0.0426 (17) | 0.068 (2) | 0.0104 (13) | 0.0134 (15) | 0.0021 (15) |
C25 | 0.0435 (15) | 0.0350 (15) | 0.0543 (19) | 0.0066 (12) | 0.0063 (14) | 0.0028 (13) |
C26 | 0.0380 (14) | 0.0365 (14) | 0.0459 (17) | 0.0033 (11) | 0.0066 (12) | 0.0024 (12) |
C27 | 0.0331 (13) | 0.0367 (14) | 0.0412 (16) | −0.0002 (11) | 0.0045 (11) | 0.0037 (12) |
C28 | 0.0387 (15) | 0.0331 (15) | 0.057 (2) | −0.0027 (12) | 0.0073 (13) | 0.0068 (13) |
C29 | 0.0458 (17) | 0.0408 (17) | 0.073 (2) | −0.0056 (13) | 0.0107 (16) | 0.0098 (15) |
C30 | 0.0400 (18) | 0.053 (2) | 0.097 (3) | −0.0058 (15) | 0.0172 (19) | 0.0113 (19) |
C31 | 0.0429 (18) | 0.056 (2) | 0.090 (3) | 0.0035 (15) | 0.0248 (18) | 0.0093 (19) |
C32 | 0.0365 (15) | 0.0381 (15) | 0.061 (2) | −0.0002 (12) | 0.0137 (14) | 0.0064 (14) |
C33 | 0.085 (3) | 0.064 (2) | 0.052 (2) | 0.003 (2) | 0.0155 (19) | 0.0069 (17) |
C34 | 0.066 (3) | 0.091 (3) | 0.070 (3) | 0.001 (2) | 0.025 (2) | 0.015 (2) |
C35 | 0.078 (3) | 0.075 (3) | 0.085 (3) | 0.014 (2) | 0.038 (2) | 0.005 (2) |
C36 | 0.093 (3) | 0.079 (3) | 0.088 (3) | −0.004 (3) | 0.042 (3) | −0.008 (2) |
C37 | 0.077 (3) | 0.107 (4) | 0.075 (3) | 0.002 (3) | 0.035 (2) | 0.012 (3) |
C38 | 0.073 (3) | 0.085 (3) | 0.063 (3) | 0.014 (2) | 0.023 (2) | 0.011 (2) |
Ni1—Br1 | 2.3390 (5) | C18—C19 | 1.518 (5) |
Ni1—P1 | 2.2223 (7) | C18—H181 | 1.000 |
Ni1—P2 | 2.1387 (8) | C18—H182 | 1.000 |
Ni1—C1 | 1.981 (3) | C19—C20 | 1.533 (4) |
Cl1—C33 | 1.719 (4) | C19—H191 | 1.000 |
P1—C7 | 1.838 (3) | C19—H192 | 1.000 |
P1—C9 | 1.848 (3) | C20—H201 | 1.000 |
P1—C15 | 1.850 (3) | C20—H202 | 1.000 |
P2—C8 | 1.851 (3) | C21—C22 | 1.543 (4) |
P2—C21 | 1.844 (3) | C21—C26 | 1.522 (4) |
P2—C27 | 1.848 (3) | C21—H211 | 1.000 |
C1—C2 | 1.400 (4) | C22—C23 | 1.532 (4) |
C1—C6 | 1.338 (4) | C22—H221 | 1.000 |
C2—C3 | 1.391 (4) | C22—H222 | 1.000 |
C2—H21 | 1.000 | C23—C24 | 1.514 (5) |
C3—C4 | 1.372 (5) | C23—H231 | 1.000 |
C3—H31 | 1.000 | C23—H232 | 1.000 |
C4—C5 | 1.381 (5) | C24—C25 | 1.518 (4) |
C4—H41 | 1.000 | C24—H241 | 1.000 |
C5—C6 | 1.399 (4) | C24—H242 | 1.000 |
C5—H51 | 1.000 | C25—C26 | 1.531 (4) |
C6—H61 | 1.000 | C25—H251 | 1.000 |
C7—C8 | 1.538 (4) | C25—H252 | 1.000 |
C7—H71 | 1.000 | C26—H261 | 1.000 |
C7—H72 | 1.000 | C26—H262 | 1.000 |
C8—H81 | 1.000 | C27—C28 | 1.537 (4) |
C8—H82 | 1.000 | C27—C32 | 1.532 (4) |
C9—C10 | 1.531 (4) | C27—H271 | 1.000 |
C9—C14 | 1.539 (4) | C28—C29 | 1.526 (4) |
C9—H91 | 1.000 | C28—H281 | 1.000 |
C10—C11 | 1.534 (4) | C28—H282 | 1.000 |
C10—H101 | 1.000 | C29—C30 | 1.526 (4) |
C10—H102 | 1.000 | C29—H291 | 1.000 |
C11—C12 | 1.525 (5) | C29—H292 | 1.000 |
C11—H111 | 1.000 | C30—C31 | 1.524 (5) |
C11—H112 | 1.000 | C30—H301 | 1.000 |
C12—C13 | 1.516 (5) | C30—H302 | 1.000 |
C12—H121 | 1.000 | C31—C32 | 1.528 (4) |
C12—H122 | 1.000 | C31—H311 | 1.000 |
C13—C14 | 1.529 (4) | C31—H312 | 1.000 |
C13—H131 | 1.000 | C32—H321 | 1.000 |
C13—H132 | 1.000 | C32—H322 | 1.000 |
C14—H141 | 1.000 | C33—C34 | 1.393 (6) |
C14—H142 | 1.000 | C33—C38 | 1.367 (6) |
C15—C16 | 1.533 (4) | C34—C35 | 1.382 (6) |
C15—C20 | 1.535 (4) | C34—H341 | 1.000 |
C15—H151 | 1.000 | C35—C36 | 1.365 (6) |
C16—C17 | 1.535 (4) | C35—H351 | 1.000 |
C16—H161 | 1.000 | C36—C37 | 1.353 (6) |
C16—H162 | 1.000 | C36—H361 | 1.000 |
C17—C18 | 1.517 (5) | C37—C38 | 1.420 (6) |
C17—H171 | 1.000 | C37—H371 | 1.000 |
C17—H172 | 1.000 | C38—H381 | 1.000 |
Br1—Ni1—P1 | 92.87 (2) | C17—C18—H182 | 109.76 (18) |
Br1—Ni1—P2 | 173.61 (3) | C19—C18—H182 | 109.28 (18) |
P1—Ni1—P2 | 89.19 (3) | H181—C18—H182 | 109.467 |
Br1—Ni1—C1 | 89.78 (7) | C18—C19—C20 | 112.3 (3) |
P1—Ni1—C1 | 170.47 (8) | C18—C19—H191 | 109.41 (18) |
P2—Ni1—C1 | 89.16 (7) | C20—C19—H191 | 109.14 (17) |
Ni1—P1—C7 | 107.89 (9) | C18—C19—H192 | 108.1 (2) |
Ni1—P1—C9 | 113.02 (9) | C20—C19—H192 | 108.40 (19) |
C7—P1—C9 | 103.90 (13) | H191—C19—H192 | 109.467 |
Ni1—P1—C15 | 123.3 (1) | C15—C20—C19 | 110.9 (2) |
C7—P1—C15 | 102.94 (13) | C15—C20—H201 | 108.56 (16) |
C9—P1—C15 | 103.85 (12) | C19—C20—H201 | 109.07 (19) |
Ni1—P2—C8 | 109.45 (9) | C15—C20—H202 | 109.29 (17) |
Ni1—P2—C21 | 113.97 (9) | C19—C20—H202 | 109.55 (18) |
C8—P2—C21 | 103.53 (12) | H201—C20—H202 | 109.467 |
Ni1—P2—C27 | 120.48 (9) | P2—C21—C22 | 111.44 (18) |
C8—P2—C27 | 103.03 (13) | P2—C21—C26 | 113.26 (19) |
C21—P2—C27 | 104.61 (12) | C22—C21—C26 | 110.6 (2) |
Ni1—C1—C2 | 114.0 (2) | P2—C21—H211 | 107.18 (8) |
Ni1—C1—C6 | 125.9 (2) | C22—C21—H211 | 107.86 (15) |
C2—C1—C6 | 120.0 (3) | C26—C21—H211 | 106.20 (15) |
C1—C2—C3 | 119.3 (3) | C21—C22—C23 | 110.1 (2) |
C1—C2—H21 | 120.07 (17) | C21—C22—H221 | 109.47 (15) |
C3—C2—H21 | 120.6 (2) | C23—C22—H221 | 110.13 (17) |
C2—C3—C4 | 120.8 (3) | C21—C22—H222 | 108.84 (15) |
C2—C3—H31 | 119.5 (2) | C23—C22—H222 | 108.85 (17) |
C4—C3—H31 | 119.69 (19) | H221—C22—H222 | 109.467 |
C3—C4—C5 | 118.9 (3) | C22—C23—C24 | 110.7 (3) |
C3—C4—H41 | 120.31 (19) | C22—C23—H231 | 108.65 (17) |
C5—C4—H41 | 120.77 (19) | C24—C23—H231 | 108.41 (18) |
C4—C5—C6 | 120.3 (3) | C22—C23—H232 | 109.91 (17) |
C4—C5—H51 | 119.90 (19) | C24—C23—H232 | 109.72 (17) |
C6—C5—H51 | 119.8 (2) | H231—C23—H232 | 109.467 |
C1—C6—C5 | 120.7 (3) | C23—C24—C25 | 112.0 (3) |
C1—C6—H61 | 119.28 (16) | C23—C24—H241 | 109.84 (16) |
C5—C6—H61 | 120.0 (2) | C25—C24—H241 | 109.44 (15) |
P1—C7—C8 | 110.43 (19) | C23—C24—H242 | 107.88 (18) |
P1—C7—H71 | 109.07 (9) | C25—C24—H242 | 108.15 (18) |
C8—C7—H71 | 109.17 (16) | H241—C24—H242 | 109.467 |
P1—C7—H72 | 109.29 (9) | C24—C25—C26 | 111.6 (2) |
C8—C7—H72 | 109.39 (14) | C24—C25—H251 | 108.26 (18) |
H71—C7—H72 | 109.467 | C26—C25—H251 | 108.72 (16) |
P2—C8—C7 | 111.46 (18) | C24—C25—H252 | 109.43 (17) |
P2—C8—H81 | 108.75 (9) | C26—C25—H252 | 109.36 (16) |
C7—C8—H81 | 109.06 (16) | H251—C25—H252 | 109.467 |
P2—C8—H82 | 109.10 (9) | C21—C26—C25 | 110.7 (2) |
C7—C8—H82 | 108.98 (15) | C21—C26—H261 | 109.12 (15) |
H81—C8—H82 | 109.467 | C25—C26—H261 | 109.53 (16) |
P1—C9—C10 | 111.44 (18) | C21—C26—H262 | 108.96 (15) |
P1—C9—C14 | 113.66 (19) | C25—C26—H262 | 109.08 (16) |
C10—C9—C14 | 110.8 (2) | H261—C26—H262 | 109.466 |
P1—C9—H91 | 106.9 (1) | P2—C27—C28 | 115.0 (2) |
C10—C9—H91 | 107.86 (17) | P2—C27—C32 | 110.65 (19) |
C14—C9—H91 | 105.77 (18) | C28—C27—C32 | 111.1 (2) |
C9—C10—C11 | 111.5 (2) | P2—C27—H271 | 106.56 (9) |
C9—C10—H101 | 109.29 (16) | C28—C27—H271 | 104.02 (16) |
C11—C10—H101 | 109.58 (17) | C32—C27—H271 | 109.11 (17) |
C9—C10—H102 | 108.18 (17) | C27—C28—C29 | 110.5 (3) |
C11—C10—H102 | 108.76 (18) | C27—C28—H281 | 108.71 (16) |
H101—C10—H102 | 109.467 | C29—C28—H281 | 108.84 (18) |
C10—C11—C12 | 111.6 (3) | C27—C28—H282 | 109.55 (15) |
C10—C11—H111 | 108.69 (18) | C29—C28—H282 | 109.75 (16) |
C12—C11—H111 | 108.2 (2) | H281—C28—H282 | 109.467 |
C10—C11—H112 | 109.34 (17) | C28—C29—C30 | 110.9 (3) |
C12—C11—H112 | 109.45 (18) | C28—C29—H291 | 109.70 (18) |
H111—C11—H112 | 109.467 | C30—C29—H291 | 109.26 (19) |
C11—C12—C13 | 111.2 (3) | C28—C29—H292 | 108.63 (18) |
C11—C12—H121 | 109.94 (17) | C30—C29—H292 | 108.8 (2) |
C13—C12—H121 | 109.81 (18) | H291—C29—H292 | 109.467 |
C11—C12—H122 | 108.3 (2) | C29—C30—C31 | 110.8 (3) |
C13—C12—H122 | 108.1 (2) | C29—C30—H301 | 108.8 (2) |
H121—C12—H122 | 109.467 | C31—C30—H301 | 108.3 (2) |
C12—C13—C14 | 111.7 (3) | C29—C30—H302 | 109.70 (18) |
C12—C13—H131 | 108.0 (2) | C31—C30—H302 | 109.7 (2) |
C14—C13—H131 | 108.4 (2) | H301—C30—H302 | 109.467 |
C12—C13—H132 | 109.8 (2) | C30—C31—C32 | 111.0 (3) |
C14—C13—H132 | 109.45 (18) | C30—C31—H311 | 109.68 (18) |
H131—C13—H132 | 109.467 | C32—C31—H311 | 110.04 (17) |
C9—C14—C13 | 110.8 (3) | C30—C31—H312 | 108.3 (2) |
C9—C14—H141 | 109.38 (16) | C32—C31—H312 | 108.3 (2) |
C13—C14—H141 | 110.01 (18) | H311—C31—H312 | 109.467 |
C9—C14—H142 | 108.48 (18) | C27—C32—C31 | 111.9 (2) |
C13—C14—H142 | 108.7 (2) | C27—C32—H321 | 108.54 (17) |
H141—C14—H142 | 109.467 | C31—C32—H321 | 108.3 (2) |
P1—C15—C16 | 114.22 (19) | C27—C32—H322 | 109.02 (15) |
P1—C15—C20 | 111.73 (19) | C31—C32—H322 | 109.58 (19) |
C16—C15—C20 | 110.0 (2) | H321—C32—H322 | 109.467 |
P1—C15—H151 | 106.04 (9) | Cl1—C33—C34 | 120.2 (3) |
C16—C15—H151 | 105.67 (17) | Cl1—C33—C38 | 118.7 (3) |
C20—C15—H151 | 108.82 (16) | C34—C33—C38 | 121.1 (4) |
C15—C16—C17 | 110.7 (3) | C33—C34—C35 | 118.0 (4) |
C15—C16—H161 | 108.18 (17) | C33—C34—H341 | 120.2 (3) |
C17—C16—H161 | 108.2 (2) | C35—C34—H341 | 121.8 (3) |
C15—C16—H162 | 109.79 (15) | C34—C35—C36 | 120.9 (4) |
C17—C16—H162 | 110.47 (17) | C34—C35—H351 | 120.2 (3) |
H161—C16—H162 | 109.467 | C36—C35—H351 | 118.9 (3) |
C16—C17—C18 | 111.4 (3) | C35—C36—C37 | 122.1 (5) |
C16—C17—H171 | 109.80 (19) | C35—C36—H361 | 119.1 (3) |
C18—C17—H171 | 110.0 (2) | C37—C36—H361 | 118.9 (3) |
C16—C17—H172 | 108.0 (2) | C36—C37—C38 | 118.1 (5) |
C18—C17—H172 | 108.2 (2) | C36—C37—H371 | 121.1 (3) |
H171—C17—H172 | 109.467 | C38—C37—H371 | 120.8 (3) |
C17—C18—C19 | 111.9 (3) | C33—C38—C37 | 119.8 (4) |
C17—C18—H181 | 108.0 (2) | C33—C38—H381 | 119.2 (3) |
C19—C18—H181 | 108.4 (2) | C37—C38—H381 | 120.9 (3) |
Experimental details
Crystal data | |
Chemical formula | [NiBr(C6H5)(C26H48P2)]·C6H5Cl |
Mr | 750.89 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 200 |
a, b, c (Å) | 11.8308 (1), 22.7790 (3), 14.5238 (2) |
β (°) | 107.4072 (5) |
V (Å3) | 3734.82 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.77 |
Crystal size (mm) | 0.20 × 0.16 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Integration (Coppens, 1970) |
Tmin, Tmax | 0.662, 0.808 |
No. of measured, independent and observed [I > 3σ(I)] reflections | 94198, 8553, 4771 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.031, 1.05 |
No. of reflections | 4771 |
No. of parameters | 446 |
No. of restraints | ? |
H-atom treatment | Only H-atom displacement parameters refined |
Δρmax, Δρmin (e Å−3) | 0.56, −0.51 |
Computer programs: COLLECT (Nonius, 1997), HKL SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Watkin et al., 2001) and maXus (Mackay et al., 1999), CAMERON (Watkin et al., 1996), CRYSTALS and maXus.
Ni1—Br1 | 2.3390 (5) | P2—C27 | 1.848 (3) |
Ni1—P1 | 2.2223 (7) | C1—C2 | 1.400 (4) |
Ni1—P2 | 2.1387 (8) | C1—C6 | 1.338 (4) |
Ni1—C1 | 1.981 (3) | C2—C3 | 1.391 (4) |
P1—C7 | 1.838 (3) | C3—C4 | 1.372 (5) |
P1—C9 | 1.848 (3) | C4—C5 | 1.381 (5) |
P1—C15 | 1.850 (3) | C5—C6 | 1.399 (4) |
P2—C8 | 1.851 (3) | C7—C8 | 1.538 (4) |
P2—C21 | 1.844 (3) | ||
Br1—Ni1—P1 | 92.87 (2) | Ni1—P1—C15 | 123.3 (1) |
Br1—Ni1—P2 | 173.61 (3) | Ni1—P2—C8 | 109.45 (9) |
P1—Ni1—P2 | 89.19 (3) | Ni1—P2—C21 | 113.97 (9) |
Br1—Ni1—C1 | 89.78 (7) | Ni1—P2—C27 | 120.48 (9) |
P1—Ni1—C1 | 170.47 (8) | Ni1—C1—C2 | 114.0 (2) |
P2—Ni1—C1 | 89.16 (7) | Ni1—C1—C6 | 125.9 (2) |
Ni1—P1—C7 | 107.89 (9) | P1—C7—C8 | 110.43 (19) |
Ni1—P1—C9 | 113.02 (9) | P2—C8—C7 | 111.46 (18) |
Arylnickel(II) complexes are usually prepared by oxidative addition of aryl halides to a nickel(0) centre. Compound (II) and related species have been obtained by reaction of bromobenzene with [Ni(η2-C2H4)(dcpe)] (Bennett et al., 1985) or with [NiBr2(PPh3)2] in the presence of activated zinc, followed by ligand exchange with dcpe (Bennett & Wenger, 1995). The present sample, however, was isolated after hydrolysis of the arylnickel(II) complex (I) bearing a boronic ester group in the ortho position. The latter complex, which has been studied as a precursor to the benzynenickel(0) complex [Ni(η2-C6H4)(dcpe)] (Bennett et al., 2002), is highly reactive towards moisture, due to the large steric interaction between the boronic ester substituent and the cyclohexyl groups on the diphosphine ligand. Cleavage of the C—B bond in (I) occurs readily and compound (II) was obtained from attempted crystallizations of (I).
Complex (II) crystallized as a chlorobenzene solvate, and the solvent molecule was clearly defined. The nickel centre of (II) is in a square-planar environment, with C1—Ni—P1 and Br1—Ni—P2 angles of 170.47 (8) and 173.61 (3)°, respectively. The Ni—P distances are not equivalent, the bond trans to atom C1 being longer than the bond trans to Br, as expected from the larger trans influence of the phenyl group. Similarly, the Ni—C1 distance [1.981 (3) Å] is longer than that in complexes having trans phosphines and a halide trans to Ni—C; see for example [NiCl(o-C6H4Me)(PPh3)2] (1.900 Å; Spek et al., 2000) and [NiCl(o-C6H4CF3)(PPh3)2] (1.890%A; Lutz et al., 1998). The other geometric data of complex (II) are unexceptional.