Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S010827010200032X/bm1484sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S010827010200032X/bm1484Isup2.hkl |
CCDC reference: 182974
All manipulations were conducted under an atmosphere of dry dinitrogen or in vacuo, using standard glove-box techniques. The solvents were dried over sodium and distilled under dinitrogen immediately prior to use. ClB(cat) (cat is 1,2-O2C6H4) was purchased from commercial sources and used without further purification. [Ni(η-C2H4)(PPh3)2] was prepared in accordance with the literature (Schramm & Ibers, 1980). A solution of ClB(cat) (0.013 g, 0.084 mmol) in toluene (ca 1 ml) was prepared in a small sample vial and then transferred to a similar vessel containing [Ni(η-C2H4)(PPh3)2] (0.046 g, 0.076 mmol). After ca 5 min at room temperature, a cloudy dark-green solution resulted. Hexane (ca 4 ml) was then added to the reaction mixture, leading to the formation of a dark-green precipitate. This was allowed to settle prior to removal and filtration of the orange mother liquors. These were concentrated in vacuo to afford an orange oil, which was further diluted with toluene (ca 1 ml) and transferred to a small Schlenk tube. A hexane overlayer was added which, upon slow solvent diffusion at 251 K, afforded yellow crystals of (I) and orange crystals of [NiCl(PPh3)3]. The latter were shown by X-ray crystallography to be isomorphous with the polymorph reported by Ellis & Spek (2000).
H atoms were constrained to idealized geometries at a distance of 0.95 Å from their parent C atoms and with Uiso(H) = 1.2Ueq(C).
Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Bruker, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. The molecular structure of the title compound with ellipsoids drawn at the 50% probability level. H atoms have been omitted for clarity. |
[NiCl(C18H15P)2] | F(000) = 1284 |
Mr = 618.70 | Dx = 1.388 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.0778 (11) Å | Cell parameters from 8192 reflections |
b = 17.535 (2) Å | θ = 2–25° |
c = 15.4159 (18) Å | µ = 0.88 mm−1 |
β = 98.722 (8)° | T = 173 K |
V = 2960.0 (6) Å3 | Plate, yellow |
Z = 4 | 0.40 × 0.25 × 0.12 mm |
Bruker SMART CCD area-detector diffractometer | 6788 independent reflections |
Radiation source: fine-focus sealed tube | 4961 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
ω scans | θmax = 27.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→14 |
Tmin = 0.720, Tmax = 0.924 | k = −22→22 |
18753 measured reflections | l = −20→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.031 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.92 | w = 1/[σ2(Fo2) + (0.034P)2] where P = (Fo2 + 2Fc2)/3 |
6788 reflections | (Δ/σ)max = 0.001 |
361 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.32 e Å−3 |
[NiCl(C18H15P)2] | V = 2960.0 (6) Å3 |
Mr = 618.70 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.0778 (11) Å | µ = 0.88 mm−1 |
b = 17.535 (2) Å | T = 173 K |
c = 15.4159 (18) Å | 0.40 × 0.25 × 0.12 mm |
β = 98.722 (8)° |
Bruker SMART CCD area-detector diffractometer | 6788 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4961 reflections with I > 2σ(I) |
Tmin = 0.720, Tmax = 0.924 | Rint = 0.035 |
18753 measured reflections |
R[F2 > 2σ(F2)] = 0.031 | 0 restraints |
wR(F2) = 0.072 | H-atom parameters constrained |
S = 0.92 | Δρmax = 0.37 e Å−3 |
6788 reflections | Δρmin = −0.32 e Å−3 |
361 parameters |
Experimental. Unit-cell dimensions were determined from reflections taken from three sets of 30 frames (at 0.3° steps in ω) at 10 s per frame. A full hemisphere of reciprocal space was scanned by 0.3° ω steps at ϕ = 0, 90 and 180° and 20 s per frame, with the area detector held at 2θ = -27°. The crystal-to-detector distance was 4.974 cm. Crystal decay was monitored by repeating the initial 50 frames at the end of data collection and analysing the duplicate reflections. No decay was observed. |
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. |
x | y | z | Uiso*/Ueq | ||
Ni1 | 0.81960 (2) | 0.196069 (12) | 0.557896 (14) | 0.01875 (7) | |
Cl1 | 0.82054 (4) | 0.07281 (3) | 0.56762 (3) | 0.03381 (12) | |
P1 | 0.98846 (4) | 0.26492 (3) | 0.60546 (3) | 0.01882 (11) | |
P2 | 0.65054 (4) | 0.26491 (3) | 0.51600 (3) | 0.02017 (11) | |
C1 | 1.04768 (16) | 0.32941 (10) | 0.52857 (11) | 0.0208 (4) | |
C2 | 0.96831 (18) | 0.35570 (12) | 0.45650 (13) | 0.0347 (5) | |
H2 | 0.8853 | 0.3399 | 0.4483 | 0.042* | |
C3 | 1.0080 (2) | 0.40445 (13) | 0.39642 (15) | 0.0484 (6) | |
H3 | 0.9523 | 0.4217 | 0.3473 | 0.058* | |
C4 | 1.1272 (2) | 0.42818 (12) | 0.40711 (14) | 0.0398 (5) | |
H4 | 1.1545 | 0.4615 | 0.3655 | 0.048* | |
C5 | 1.20709 (19) | 0.40317 (11) | 0.47903 (14) | 0.0354 (5) | |
H5 | 1.2895 | 0.4200 | 0.4873 | 0.042* | |
C6 | 1.16834 (17) | 0.35405 (11) | 0.53879 (13) | 0.0307 (5) | |
H6 | 1.2246 | 0.3368 | 0.5875 | 0.037* | |
C11 | 1.11895 (16) | 0.20166 (10) | 0.64110 (11) | 0.0205 (4) | |
C12 | 1.21097 (17) | 0.22057 (11) | 0.71007 (12) | 0.0260 (4) | |
H12 | 1.2050 | 0.2662 | 0.7424 | 0.031* | |
C13 | 1.31122 (17) | 0.17281 (11) | 0.73151 (13) | 0.0303 (5) | |
H13 | 1.3737 | 0.1859 | 0.7784 | 0.036* | |
C14 | 1.32003 (17) | 0.10645 (11) | 0.68483 (13) | 0.0306 (5) | |
H14 | 1.3892 | 0.0743 | 0.6992 | 0.037* | |
C15 | 1.22874 (17) | 0.08652 (11) | 0.61731 (13) | 0.0293 (4) | |
H15 | 1.2345 | 0.0404 | 0.5858 | 0.035* | |
C16 | 1.12844 (16) | 0.13414 (10) | 0.59558 (12) | 0.0256 (4) | |
H16 | 1.0658 | 0.1204 | 0.5491 | 0.031* | |
C21 | 0.98375 (15) | 0.32423 (10) | 0.70235 (11) | 0.0207 (4) | |
C22 | 0.94466 (17) | 0.29060 (11) | 0.77540 (12) | 0.0291 (4) | |
H22 | 0.9234 | 0.2381 | 0.7739 | 0.035* | |
C23 | 0.93656 (18) | 0.33313 (12) | 0.85008 (12) | 0.0328 (5) | |
H23 | 0.9105 | 0.3094 | 0.8995 | 0.039* | |
C24 | 0.96602 (17) | 0.40968 (11) | 0.85319 (12) | 0.0296 (5) | |
H24 | 0.9593 | 0.4388 | 0.9042 | 0.036* | |
C25 | 1.00539 (17) | 0.44373 (11) | 0.78157 (12) | 0.0289 (4) | |
H25 | 1.0264 | 0.4963 | 0.7836 | 0.035* | |
C26 | 1.01428 (16) | 0.40136 (10) | 0.70662 (12) | 0.0250 (4) | |
H26 | 1.0415 | 0.4253 | 0.6578 | 0.030* | |
C31 | 0.64480 (16) | 0.33238 (11) | 0.42463 (11) | 0.0232 (4) | |
C32 | 0.6162 (2) | 0.40922 (11) | 0.42925 (13) | 0.0366 (5) | |
H32 | 0.5934 | 0.4294 | 0.4816 | 0.044* | |
C33 | 0.6208 (2) | 0.45700 (13) | 0.35750 (15) | 0.0480 (6) | |
H33 | 0.6015 | 0.5096 | 0.3614 | 0.058* | |
C34 | 0.6530 (2) | 0.42846 (14) | 0.28090 (14) | 0.0446 (6) | |
H34 | 0.6577 | 0.4615 | 0.2327 | 0.053* | |
C35 | 0.67834 (19) | 0.35204 (13) | 0.27457 (13) | 0.0387 (5) | |
H35 | 0.6985 | 0.3320 | 0.2213 | 0.046* | |
C36 | 0.67456 (17) | 0.30394 (12) | 0.34581 (12) | 0.0294 (4) | |
H36 | 0.6924 | 0.2513 | 0.3409 | 0.035* | |
C41 | 0.51249 (16) | 0.20842 (10) | 0.47999 (11) | 0.0227 (4) | |
C42 | 0.51788 (17) | 0.12966 (11) | 0.47687 (12) | 0.0279 (4) | |
H42 | 0.5929 | 0.1042 | 0.4961 | 0.033* | |
C43 | 0.41386 (18) | 0.08744 (12) | 0.44566 (13) | 0.0327 (5) | |
H43 | 0.4185 | 0.0334 | 0.4424 | 0.039* | |
C44 | 0.30396 (18) | 0.12399 (12) | 0.41940 (12) | 0.0334 (5) | |
H44 | 0.2330 | 0.0950 | 0.3986 | 0.040* | |
C45 | 0.29703 (17) | 0.20234 (12) | 0.42333 (12) | 0.0322 (5) | |
H45 | 0.2211 | 0.2273 | 0.4059 | 0.039* | |
C46 | 0.40103 (17) | 0.24491 (11) | 0.45270 (12) | 0.0289 (4) | |
H46 | 0.3963 | 0.2990 | 0.4542 | 0.035* | |
C51 | 0.61319 (16) | 0.32193 (10) | 0.60753 (11) | 0.0210 (4) | |
C52 | 0.51643 (17) | 0.30485 (10) | 0.65235 (12) | 0.0262 (4) | |
H52 | 0.4611 | 0.2651 | 0.6318 | 0.031* | |
C53 | 0.50072 (19) | 0.34566 (11) | 0.72674 (13) | 0.0320 (5) | |
H53 | 0.4347 | 0.3335 | 0.7571 | 0.038* | |
C54 | 0.57992 (18) | 0.40366 (11) | 0.75712 (13) | 0.0312 (5) | |
H54 | 0.5684 | 0.4314 | 0.8082 | 0.037* | |
C55 | 0.67622 (17) | 0.42144 (11) | 0.71310 (12) | 0.0290 (4) | |
H55 | 0.7305 | 0.4617 | 0.7336 | 0.035* | |
C56 | 0.69326 (16) | 0.38068 (10) | 0.63953 (12) | 0.0249 (4) | |
H56 | 0.7603 | 0.3926 | 0.6101 | 0.030* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni1 | 0.01897 (13) | 0.01748 (12) | 0.01960 (12) | −0.00112 (10) | 0.00228 (8) | 0.00032 (9) |
Cl1 | 0.0304 (3) | 0.0192 (2) | 0.0501 (3) | −0.0012 (2) | 0.0008 (2) | 0.0045 (2) |
P1 | 0.0190 (2) | 0.0192 (2) | 0.0181 (2) | −0.00103 (19) | 0.00204 (17) | −0.00008 (18) |
P2 | 0.0181 (2) | 0.0203 (2) | 0.0218 (2) | −0.00096 (19) | 0.00228 (18) | −0.00031 (19) |
C1 | 0.0225 (10) | 0.0192 (9) | 0.0211 (9) | −0.0015 (8) | 0.0051 (7) | −0.0011 (7) |
C2 | 0.0269 (11) | 0.0399 (12) | 0.0350 (11) | −0.0106 (9) | −0.0030 (8) | 0.0113 (10) |
C3 | 0.0452 (15) | 0.0539 (15) | 0.0422 (13) | −0.0127 (12) | −0.0060 (11) | 0.0246 (12) |
C4 | 0.0451 (14) | 0.0350 (12) | 0.0411 (13) | −0.0067 (10) | 0.0125 (10) | 0.0127 (10) |
C5 | 0.0267 (11) | 0.0331 (12) | 0.0487 (13) | −0.0045 (9) | 0.0132 (9) | 0.0052 (10) |
C6 | 0.0240 (11) | 0.0333 (11) | 0.0342 (11) | −0.0010 (9) | 0.0027 (8) | 0.0066 (9) |
C11 | 0.0194 (9) | 0.0215 (9) | 0.0207 (9) | −0.0026 (7) | 0.0034 (7) | 0.0033 (7) |
C12 | 0.0266 (10) | 0.0256 (10) | 0.0249 (10) | −0.0013 (8) | 0.0010 (8) | −0.0017 (8) |
C13 | 0.0250 (11) | 0.0335 (11) | 0.0297 (11) | −0.0015 (9) | −0.0048 (8) | 0.0033 (9) |
C14 | 0.0248 (11) | 0.0278 (11) | 0.0389 (12) | 0.0035 (9) | 0.0043 (8) | 0.0096 (9) |
C15 | 0.0301 (11) | 0.0250 (10) | 0.0339 (11) | 0.0024 (9) | 0.0081 (8) | −0.0018 (9) |
C16 | 0.0248 (10) | 0.0275 (10) | 0.0242 (10) | −0.0011 (8) | 0.0023 (7) | −0.0007 (8) |
C21 | 0.0184 (9) | 0.0238 (10) | 0.0192 (9) | −0.0010 (7) | 0.0010 (7) | −0.0017 (7) |
C22 | 0.0345 (12) | 0.0275 (11) | 0.0259 (10) | −0.0048 (9) | 0.0068 (8) | −0.0001 (8) |
C23 | 0.0381 (12) | 0.0391 (12) | 0.0221 (10) | −0.0021 (10) | 0.0076 (8) | 0.0009 (9) |
C24 | 0.0302 (11) | 0.0363 (12) | 0.0212 (10) | 0.0054 (9) | −0.0001 (8) | −0.0066 (8) |
C25 | 0.0332 (11) | 0.0235 (10) | 0.0277 (10) | 0.0000 (9) | −0.0021 (8) | −0.0038 (8) |
C26 | 0.0269 (10) | 0.0247 (10) | 0.0230 (10) | −0.0005 (8) | 0.0030 (7) | −0.0012 (8) |
C31 | 0.0172 (9) | 0.0275 (10) | 0.0239 (10) | −0.0037 (8) | 0.0002 (7) | 0.0015 (8) |
C32 | 0.0498 (14) | 0.0302 (11) | 0.0293 (11) | 0.0051 (10) | 0.0047 (9) | 0.0032 (9) |
C33 | 0.0683 (17) | 0.0314 (12) | 0.0408 (14) | 0.0028 (12) | −0.0033 (12) | 0.0104 (10) |
C34 | 0.0460 (14) | 0.0536 (15) | 0.0306 (12) | −0.0127 (12) | −0.0054 (10) | 0.0171 (11) |
C35 | 0.0341 (12) | 0.0561 (15) | 0.0251 (11) | −0.0082 (11) | 0.0016 (9) | 0.0037 (10) |
C36 | 0.0244 (10) | 0.0373 (12) | 0.0255 (10) | −0.0030 (9) | 0.0008 (8) | −0.0017 (9) |
C41 | 0.0204 (10) | 0.0270 (10) | 0.0207 (9) | −0.0024 (8) | 0.0029 (7) | 0.0006 (8) |
C42 | 0.0223 (10) | 0.0293 (11) | 0.0316 (11) | −0.0010 (8) | 0.0021 (8) | 0.0013 (9) |
C43 | 0.0324 (12) | 0.0287 (11) | 0.0365 (12) | −0.0087 (9) | 0.0033 (9) | −0.0012 (9) |
C44 | 0.0243 (11) | 0.0466 (13) | 0.0283 (11) | −0.0139 (10) | 0.0014 (8) | −0.0002 (9) |
C45 | 0.0202 (10) | 0.0472 (13) | 0.0285 (11) | −0.0012 (9) | 0.0011 (8) | 0.0048 (9) |
C46 | 0.0263 (11) | 0.0307 (11) | 0.0288 (10) | 0.0004 (9) | 0.0016 (8) | 0.0013 (8) |
C51 | 0.0189 (9) | 0.0216 (9) | 0.0219 (9) | 0.0036 (7) | 0.0011 (7) | 0.0024 (7) |
C52 | 0.0268 (10) | 0.0243 (10) | 0.0279 (10) | −0.0021 (8) | 0.0052 (8) | 0.0014 (8) |
C53 | 0.0358 (12) | 0.0323 (11) | 0.0310 (11) | −0.0008 (9) | 0.0151 (9) | 0.0038 (9) |
C54 | 0.0405 (12) | 0.0296 (11) | 0.0246 (10) | 0.0038 (10) | 0.0089 (8) | −0.0026 (8) |
C55 | 0.0294 (11) | 0.0267 (11) | 0.0299 (11) | 0.0010 (9) | 0.0014 (8) | −0.0043 (8) |
C56 | 0.0198 (10) | 0.0269 (10) | 0.0283 (10) | 0.0006 (8) | 0.0050 (7) | −0.0012 (8) |
Ni1—Cl1 | 2.1666 (6) | C24—H24 | 0.9500 |
Ni1—P2 | 2.2393 (5) | C25—C26 | 1.390 (2) |
Ni1—P1 | 2.2536 (5) | C25—H25 | 0.9500 |
P1—C21 | 1.8274 (18) | C26—H26 | 0.9500 |
P1—C1 | 1.8302 (18) | C31—C32 | 1.388 (3) |
P1—C11 | 1.8388 (18) | C31—C36 | 1.398 (3) |
P2—C51 | 1.8273 (19) | C32—C33 | 1.395 (3) |
P2—C31 | 1.8333 (19) | C32—H32 | 0.9500 |
P2—C41 | 1.8359 (18) | C33—C34 | 1.379 (3) |
C1—C2 | 1.387 (2) | C33—H33 | 0.9500 |
C1—C6 | 1.391 (2) | C34—C35 | 1.376 (3) |
C2—C3 | 1.380 (3) | C34—H34 | 0.9500 |
C2—H2 | 0.9500 | C35—C36 | 1.390 (3) |
C3—C4 | 1.371 (3) | C35—H35 | 0.9500 |
C3—H3 | 0.9500 | C36—H36 | 0.9500 |
C4—C5 | 1.381 (3) | C41—C42 | 1.384 (2) |
C4—H4 | 0.9500 | C41—C46 | 1.398 (2) |
C5—C6 | 1.376 (3) | C42—C43 | 1.393 (2) |
C5—H5 | 0.9500 | C42—H42 | 0.9500 |
C6—H6 | 0.9500 | C43—C44 | 1.381 (3) |
C11—C16 | 1.388 (2) | C43—H43 | 0.9500 |
C11—C12 | 1.397 (2) | C44—C45 | 1.378 (3) |
C12—C13 | 1.390 (3) | C44—H44 | 0.9500 |
C12—H12 | 0.9500 | C45—C46 | 1.390 (3) |
C13—C14 | 1.379 (3) | C45—H45 | 0.9500 |
C13—H13 | 0.9500 | C46—H46 | 0.9500 |
C14—C15 | 1.382 (3) | C51—C52 | 1.393 (3) |
C14—H14 | 0.9500 | C51—C56 | 1.400 (2) |
C15—C16 | 1.390 (2) | C52—C53 | 1.385 (3) |
C15—H15 | 0.9500 | C52—H52 | 0.9500 |
C16—H16 | 0.9500 | C53—C54 | 1.378 (3) |
C21—C26 | 1.393 (2) | C53—H53 | 0.9500 |
C21—C22 | 1.397 (3) | C54—C55 | 1.384 (3) |
C22—C23 | 1.386 (3) | C54—H54 | 0.9500 |
C22—H22 | 0.9500 | C55—C56 | 1.378 (3) |
C23—C24 | 1.381 (3) | C55—H55 | 0.9500 |
C23—H23 | 0.9500 | C56—H56 | 0.9500 |
C24—C25 | 1.383 (3) | ||
Cl1—Ni1—P1 | 121.12 (2) | C25—C24—H24 | 120.2 |
Cl1—Ni1—P2 | 123.56 (2) | C24—C25—C26 | 120.25 (18) |
P1—Ni1—P2 | 114.94 (2) | C24—C25—H25 | 119.9 |
C21—P1—C1 | 103.60 (8) | C26—C25—H25 | 119.9 |
C21—P1—C11 | 102.58 (8) | C25—C26—C21 | 120.73 (18) |
C1—P1—C11 | 102.91 (8) | C25—C26—H26 | 119.6 |
C21—P1—Ni1 | 116.47 (6) | C21—C26—H26 | 119.6 |
C1—P1—Ni1 | 118.79 (6) | C32—C31—C36 | 118.45 (18) |
C11—P1—Ni1 | 110.50 (6) | C32—C31—P2 | 124.64 (15) |
C51—P2—C31 | 104.75 (8) | C36—C31—P2 | 116.89 (15) |
C51—P2—C41 | 104.65 (8) | C31—C32—C33 | 120.4 (2) |
C31—P2—C41 | 100.70 (8) | C31—C32—H32 | 119.8 |
C51—P2—Ni1 | 110.47 (6) | C33—C32—H32 | 119.8 |
C31—P2—Ni1 | 119.97 (6) | C34—C33—C32 | 120.4 (2) |
C41—P2—Ni1 | 114.72 (6) | C34—C33—H33 | 119.8 |
C2—C1—C6 | 117.97 (17) | C32—C33—H33 | 119.8 |
C2—C1—P1 | 118.57 (14) | C35—C34—C33 | 119.8 (2) |
C6—C1—P1 | 123.46 (13) | C35—C34—H34 | 120.1 |
C3—C2—C1 | 121.05 (18) | C33—C34—H34 | 120.1 |
C3—C2—H2 | 119.5 | C34—C35—C36 | 120.3 (2) |
C1—C2—H2 | 119.5 | C34—C35—H35 | 119.9 |
C4—C3—C2 | 120.42 (19) | C36—C35—H35 | 119.9 |
C4—C3—H3 | 119.8 | C35—C36—C31 | 120.6 (2) |
C2—C3—H3 | 119.8 | C35—C36—H36 | 119.7 |
C3—C4—C5 | 119.2 (2) | C31—C36—H36 | 119.7 |
C3—C4—H4 | 120.4 | C42—C41—C46 | 119.16 (16) |
C5—C4—H4 | 120.4 | C42—C41—P2 | 120.72 (13) |
C6—C5—C4 | 120.60 (19) | C46—C41—P2 | 120.09 (14) |
C6—C5—H5 | 119.7 | C41—C42—C43 | 120.33 (17) |
C4—C5—H5 | 119.7 | C41—C42—H42 | 119.8 |
C5—C6—C1 | 120.70 (18) | C43—C42—H42 | 119.8 |
C5—C6—H6 | 119.6 | C44—C43—C42 | 120.07 (19) |
C1—C6—H6 | 119.6 | C44—C43—H43 | 120.0 |
C16—C11—C12 | 119.00 (16) | C42—C43—H43 | 120.0 |
C16—C11—P1 | 118.67 (13) | C45—C44—C43 | 120.16 (18) |
C12—C11—P1 | 122.28 (14) | C45—C44—H44 | 119.9 |
C13—C12—C11 | 120.16 (17) | C43—C44—H44 | 119.9 |
C13—C12—H12 | 119.9 | C44—C45—C46 | 120.06 (18) |
C11—C12—H12 | 119.9 | C44—C45—H45 | 120.0 |
C14—C13—C12 | 120.09 (17) | C46—C45—H45 | 120.0 |
C14—C13—H13 | 120.0 | C45—C46—C41 | 120.20 (19) |
C12—C13—H13 | 120.0 | C45—C46—H46 | 119.9 |
C13—C14—C15 | 120.32 (18) | C41—C46—H46 | 119.9 |
C13—C14—H14 | 119.8 | C52—C51—C56 | 118.53 (17) |
C15—C14—H14 | 119.8 | C52—C51—P2 | 123.14 (14) |
C14—C15—C16 | 119.78 (18) | C56—C51—P2 | 117.99 (14) |
C14—C15—H15 | 120.1 | C53—C52—C51 | 120.16 (18) |
C16—C15—H15 | 120.1 | C53—C52—H52 | 119.9 |
C11—C16—C15 | 120.64 (16) | C51—C52—H52 | 119.9 |
C11—C16—H16 | 119.7 | C54—C53—C52 | 120.62 (19) |
C15—C16—H16 | 119.7 | C54—C53—H53 | 119.7 |
C26—C21—C22 | 118.32 (17) | C52—C53—H53 | 119.7 |
C26—C21—P1 | 123.67 (14) | C53—C54—C55 | 119.86 (19) |
C22—C21—P1 | 117.99 (14) | C53—C54—H54 | 120.1 |
C23—C22—C21 | 120.63 (18) | C55—C54—H54 | 120.1 |
C23—C22—H22 | 119.7 | C56—C55—C54 | 119.93 (18) |
C21—C22—H22 | 119.7 | C56—C55—H55 | 120.0 |
C24—C23—C22 | 120.48 (19) | C54—C55—H55 | 120.0 |
C24—C23—H23 | 119.8 | C55—C56—C51 | 120.89 (18) |
C22—C23—H23 | 119.8 | C55—C56—H56 | 119.6 |
C23—C24—C25 | 119.59 (18) | C51—C56—H56 | 119.6 |
C23—C24—H24 | 120.2 | ||
Cl1—Ni1—P1—C21 | −111.54 (7) | C21—C22—C23—C24 | 0.6 (3) |
P2—Ni1—P1—C21 | 61.66 (7) | C22—C23—C24—C25 | −0.9 (3) |
Cl1—Ni1—P1—C1 | 123.48 (7) | C23—C24—C25—C26 | 0.6 (3) |
P2—Ni1—P1—C1 | −63.33 (7) | C24—C25—C26—C21 | 0.0 (3) |
Cl1—Ni1—P1—C11 | 4.94 (7) | C22—C21—C26—C25 | −0.3 (3) |
P2—Ni1—P1—C11 | 178.14 (6) | P1—C21—C26—C25 | 178.16 (14) |
Cl1—Ni1—P2—C51 | 112.48 (7) | C51—P2—C31—C32 | −0.58 (18) |
P1—Ni1—P2—C51 | −60.53 (7) | C41—P2—C31—C32 | 107.84 (17) |
Cl1—Ni1—P2—C31 | −125.59 (7) | Ni1—P2—C31—C32 | −125.28 (15) |
P1—Ni1—P2—C31 | 61.40 (7) | C51—P2—C31—C36 | 177.73 (14) |
Cl1—Ni1—P2—C41 | −5.50 (7) | C41—P2—C31—C36 | −73.85 (15) |
P1—Ni1—P2—C41 | −178.51 (6) | Ni1—P2—C31—C36 | 53.04 (15) |
C21—P1—C1—C2 | −107.73 (16) | C36—C31—C32—C33 | −1.8 (3) |
C11—P1—C1—C2 | 145.69 (16) | P2—C31—C32—C33 | 176.46 (16) |
Ni1—P1—C1—C2 | 23.28 (18) | C31—C32—C33—C34 | 0.4 (3) |
C21—P1—C1—C6 | 71.82 (17) | C32—C33—C34—C35 | 1.4 (3) |
C11—P1—C1—C6 | −34.76 (17) | C33—C34—C35—C36 | −1.6 (3) |
Ni1—P1—C1—C6 | −157.17 (14) | C34—C35—C36—C31 | 0.1 (3) |
C6—C1—C2—C3 | 0.4 (3) | C32—C31—C36—C35 | 1.6 (3) |
P1—C1—C2—C3 | 179.97 (18) | P2—C31—C36—C35 | −176.84 (14) |
C1—C2—C3—C4 | −0.2 (4) | C51—P2—C41—C42 | −123.57 (16) |
C2—C3—C4—C5 | −0.4 (4) | C31—P2—C41—C42 | 127.93 (16) |
C3—C4—C5—C6 | 1.0 (3) | Ni1—P2—C41—C42 | −2.35 (17) |
C4—C5—C6—C1 | −0.8 (3) | C51—P2—C41—C46 | 58.45 (16) |
C2—C1—C6—C5 | 0.1 (3) | C31—P2—C41—C46 | −50.05 (17) |
P1—C1—C6—C5 | −179.42 (16) | Ni1—P2—C41—C46 | 179.67 (13) |
C21—P1—C11—C16 | 160.61 (15) | C46—C41—C42—C43 | 1.0 (3) |
C1—P1—C11—C16 | −92.03 (16) | P2—C41—C42—C43 | −177.04 (15) |
Ni1—P1—C11—C16 | 35.79 (16) | C41—C42—C43—C44 | −1.4 (3) |
C21—P1—C11—C12 | −21.88 (17) | C42—C43—C44—C45 | 0.5 (3) |
C1—P1—C11—C12 | 85.48 (17) | C43—C44—C45—C46 | 0.8 (3) |
Ni1—P1—C11—C12 | −146.70 (14) | C44—C45—C46—C41 | −1.3 (3) |
C16—C11—C12—C13 | 1.0 (3) | C42—C41—C46—C45 | 0.4 (3) |
P1—C11—C12—C13 | −176.49 (14) | P2—C41—C46—C45 | 178.38 (15) |
C11—C12—C13—C14 | −0.1 (3) | C31—P2—C51—C52 | 123.00 (15) |
C12—C13—C14—C15 | −0.8 (3) | C41—P2—C51—C52 | 17.50 (17) |
C13—C14—C15—C16 | 0.9 (3) | Ni1—P2—C51—C52 | −106.49 (14) |
C12—C11—C16—C15 | −0.9 (3) | C31—P2—C51—C56 | −63.77 (15) |
P1—C11—C16—C15 | 176.66 (14) | C41—P2—C51—C56 | −169.27 (13) |
C14—C15—C16—C11 | 0.0 (3) | Ni1—P2—C51—C56 | 66.74 (14) |
C1—P1—C21—C26 | 3.07 (17) | C56—C51—C52—C53 | 0.1 (3) |
C11—P1—C21—C26 | 109.91 (15) | P2—C51—C52—C53 | 173.33 (14) |
Ni1—P1—C21—C26 | −129.30 (14) | C51—C52—C53—C54 | 0.3 (3) |
C1—P1—C21—C22 | −178.44 (14) | C52—C53—C54—C55 | 0.0 (3) |
C11—P1—C21—C22 | −71.60 (15) | C53—C54—C55—C56 | −0.6 (3) |
Ni1—P1—C21—C22 | 49.19 (15) | C54—C55—C56—C51 | 1.0 (3) |
C26—C21—C22—C23 | 0.0 (3) | C52—C51—C56—C55 | −0.8 (3) |
P1—C21—C22—C23 | −178.55 (15) | P2—C51—C56—C55 | −174.31 (14) |
Experimental details
Crystal data | |
Chemical formula | [NiCl(C18H15P)2] |
Mr | 618.70 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 11.0778 (11), 17.535 (2), 15.4159 (18) |
β (°) | 98.722 (8) |
V (Å3) | 2960.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.40 × 0.25 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.720, 0.924 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 18753, 6788, 4961 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.031, 0.072, 0.92 |
No. of reflections | 6788 |
No. of parameters | 361 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.32 |
Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXTL (Bruker, 1997), SHELXTL.
Ni1—Cl1 | 2.1666 (6) | Ni1—P1 | 2.2536 (5) |
Ni1—P2 | 2.2393 (5) | ||
Cl1—Ni1—P1 | 121.12 (2) | P1—Ni1—P2 | 114.94 (2) |
Cl1—Ni1—P2 | 123.56 (2) |
Although little evidence has been presented to confirm the existence of a nickel(II)–boryl compound, nickel(0) (Suginome et al., 1998) and nickel(II) (Gridnev et al., 1993) complexes have been shown to catalyse certain alkyne boration reactions by mechanisms which are proposed to involve such species. As part of our continuing studies into the syntheses of transition metal–boryl complexes, we therefore attempted a direct stoichiometric preparation. The reaction between B-chlorocatecholborane and bis(triphenylphosphine)ethenenickel(0) failed to afford the desired oxidative–addition product, instead yielding bis(triphenylphosphine)nickel(I) chloride, (I), and tris(triphenylphosphine)nickel(I) chloride as part of a product mixture (Whittell, 2000).
Complexes of nickel(I) are far less numerous than those of either nickel(0) or nickel(II), with most of those isolated as solids containing phosphine or arsine ligands (Sacconi et al., 1987). Of those containing halide ions and monodentate phosphines, only [NiX(PPh3)3] (X = Cl, Br) had been characterized by X-ray crystallography prior to this study (Cassidy & Whitmire, 1991; Mealli et al., 1983). Both of these compounds dissociate in benzene solution to afford the title compound (Heimbach, 1964) and its bromide analogue (Porri et al., 1967), respectively, in addition to free triphenylphosphine. While this manuscript was in preparation, a new polymorph of [NiCl(PPh3)3] was reported, along with the crystal structure of a tetrahydrofuran (THF) solvate of (I) (Ellis & Spek, 2000). The latter contains no short intermolecular interactions. Although not characterized crystallographically, other compounds of the formulation [NiX(PR3)2] have been studied by different analytical techniques, but these are reported to be either oligomeric (X = Cl, Br; R = Ph; Lappert & Speier, 1974; Cundy & Nöth, 1971) or dimeric with a square-planar configuration (X = Cl, Br; R = Cy; Aresta et al., 1975) in the solid state.
Consistent with the findings of Ellis & Spek (2000), complex (I) is monomeric in the crystal, with the nickel(I) coordination geometry being best described as distorted trigonal–planar (Fig. 1). This is particularly noteworthy as the formally 15-electron species might well be expected to oligomerize, as previously suggested (Lappert & Speier, 1974). The Ni—Cl bond length [2.1669 (6) Å] is comparable to that observed in [NiCl(PPh3)2]·THF [2.1481 (6) Å], but significantly shorter than in both polymorphs of [NiCl(PPh3)3] [2.2785 (9) and 2.2933 (17) Å; Cassidy & Whitmire, 1991; Ellis & Spek, 2000]. The Ni—P distances [2.2532 (6) and 2.2393 (6) Å] and Cl—Ni—P angles [123.55 (2) and 121.13 (2)°] in (I) differ significantly from one another, and are also different to the corresponding parameters in [NiCl(PPh3)2]·THF [2.2091 (6) and 2.2012 (6) Å, and 126.98 (2) and 121.33 (2)°, respectively], which also has crystallographically independent triphenylphosphine ligands. This distortion of the trigonal plane is consistent with the chemical inequivalence of the phosphorus nuclei as suggested by electron spin resonance studies on a single-crystal of [CuBr(PPh3)2] doped with (I) (Nilges et al., 1977). A distorted trigonal–planar geometry is also apparent in [Ni{N(SiMe3)2}(PPh3)2] (Bradley et al., 1972), although the Ni—P bond lengths [2.220 (4) and 2.213 (4) Å] are equivalent. These, however, are both significantly shorter than those in (I) and longer than in [NiCl(PPh3)2]·THF. Nonetheless, common to all three complexes is a contraction of the P—Ni—P angle relative to the ideal value (120°); 114.95 (2), 111.52 (2) and 107.0 (2)° for (I), [NiCl(PPh3)2]·THF and [Ni{N(SiMe3)2}(PPh3)2], respectively. A review article by Eller et al. (1977) inferred this to mean, in the case of the NiI–amide complex, that the amide was of larger steric bulk than the triphenylphosphine ligands, an assertion which is not consistent with the presence of this same structural feature in both (I) and [NiCl(PPh3)2]·THF. Consideration of steric factors alone would predict a P—Ni—P angle for all three complexes greater than 120°, as observed for the P—Cu—P angle [126.0 (1)°] in the copper(I) bromide analogue, [CuBr(PPh3)2] (Davis et al., 1973), the molecular structure of which would be expected to be determined solely by steric effects on account of the d10 electron configuration at copper. The angular distortion most probably arises from a first-order Jahn–Teller effect which, for a d9 metal complex, is expected to destabilize an ML3 structure from D3 h to C2v symmetry (Albright et al., 1985).