Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101003961/gg1036sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003961/gg1036C150sup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003961/gg1036C293sup3.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270101003961/gg1036A150sup4.hkl |
CCDC references: 166965; 166966; 166967
For related literature, see: di Vaira Midolini Sacconi (1981); Allen & Kennard (1993); Busby et al. (1993); Davies et al. (1998); Fletcher et al. (1996); Girolami et al. (1985); Itatani & Bailar (1967); Spek (1990); Spek et al. (1987).
trans-1,2-Bis(diphenylphosphino)ethene (114 mg, 0.288 mmol), nickel chloride hexahydrate (68 mg, 0.286 mmol) and ethanol (10 ml) were placed in a 23 ml Parr bomb. After sealing, the bomb was heated at 100°Ch-1 to 423 K and maintained at this temperature for 48 h. Thereafter the bomb was cooled to 293 K at a rate of 5 °Ch-1. After opening, the brown yellow crystals were collected by filtration, washed with ethanol and air dried to afford C as an analytically pure solid.
Found C 59.1, H 4.5% (C26H24Cl2NiP2 requires C 59.2, H, 4.6%). IR (KBr) 1638m, 1618m, 1476w, 1433 s, 1406w, 1385w, 1306w, 1274w, 1186w, 1160w, 1129w, 1102 s, 1069s h, 1025w, 997w, 875w, 847w, 813m, 782w, 748 s, 717 s, 704m, 689 s, and 652w (cm-1). 1H NMR (250 MHz, CDCl3) δH 8.0 m and 7.5 m (20H) and 2.1 m (4H): c.f. footnote a, Table 1 of Davies et al. (1998).
The room temperature structure of C was solved initially simply by extracting feasible positions for non-H from a difference map phased by placing Ni at the origin of the space group I2/m. This readily produced an image of a pair of superposed molecules and it was comparatively easy to select one of these and continue refinement in the true space group (I2). The coordinates thus derived were used along with appropriately modified cell dimension as starting parameters for the refinement of the 150 K structure of C. Starting parameters for the refinement of A(150) were likewise taken from the literature data (PIFDUD: Busby et al., 1993). In all three refinements H were placed in calculated positions and refined with a riding model with Ueq 1.2 x Uiso of the C to which they were attached. The absolute structures of C(150) and C(293) are based on 1170 and 1187 Friedel pairs, respectively.
For all compounds, 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: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
[NiCl2(C26H24P2)] | F(000) = 544 |
Mr = 528.0 | Dx = 1.406 Mg m−3 |
Monoclinic, I2 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.4551 (14) Å | Cell parameters from 5686 reflections |
b = 7.9901 (8) Å | θ = 3.0–27.5° |
c = 13.0350 (19) Å | µ = 1.13 mm−1 |
β = 105.983 (5)° | T = 150 K |
V = 1247.1 (3) Å3 | Needle, brown yellow |
Z = 2 | 0.20 × 0.03 × 0.03 mm |
Kappa-CCD diffractometer | 2686 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1946 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ and ω scans | h = −15→12 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −8→10 |
Tmin = 0.887, Tmax = 0.999 | l = −13→16 |
5686 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.105 | w = 1/[σ2(Fo2) + (0.0296P)2 + 0.0327P] where P = (Fo2 + 2Fc2)/3 |
S = 1.04 | (Δ/σ)max < 0.001 |
2686 reflections | Δρmax = 0.54 e Å−3 |
141 parameters | Δρmin = −0.58 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.01 (2) |
[NiCl2(C26H24P2)] | V = 1247.1 (3) Å3 |
Mr = 528.0 | Z = 2 |
Monoclinic, I2 | Mo Kα radiation |
a = 12.4551 (14) Å | µ = 1.13 mm−1 |
b = 7.9901 (8) Å | T = 150 K |
c = 13.0350 (19) Å | 0.20 × 0.03 × 0.03 mm |
β = 105.983 (5)° |
Kappa-CCD diffractometer | 2686 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1946 reflections with I > 2σ(I) |
Tmin = 0.887, Tmax = 0.999 | Rint = 0.064 |
5686 measured reflections |
R[F2 > 2σ(F2)] = 0.050 | H-atom parameters constrained |
wR(F2) = 0.105 | Δρmax = 0.54 e Å−3 |
S = 1.04 | Δρmin = −0.58 e Å−3 |
2686 reflections | Absolute structure: (Flack, 1983) |
141 parameters | Absolute structure parameter: 0.01 (2) |
1 restraint |
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 placed in calculated positions and refined with a riding model. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.0000 | 0.00232 (10) | 0.0000 | 0.0292 (2) | |
Cl | −0.12373 (12) | 0.18440 (10) | 0.02446 (11) | 0.0361 (4) | |
P | −0.11397 (13) | −0.19118 (12) | 0.01230 (11) | 0.0328 (4) | |
C1 | −0.0589 (4) | −0.3925 (5) | −0.0186 (5) | 0.0511 (15) | |
H1A | −0.0895 | −0.4844 | 0.0159 | 0.061* | |
H1B | −0.0823 | −0.4114 | −0.0967 | 0.061* | |
C2 | −0.1253 (4) | −0.2100 (5) | 0.1465 (4) | 0.0335 (11) | |
C3 | −0.0519 (4) | −0.1211 (6) | 0.2281 (4) | 0.0381 (11) | |
H3 | 0.0042 | −0.0532 | 0.2125 | 0.046* | |
C4 | −0.0598 (4) | −0.1304 (6) | 0.3316 (4) | 0.0463 (13) | |
H4 | −0.0094 | −0.0685 | 0.3864 | 0.056* | |
C5 | −0.1396 (5) | −0.2279 (6) | 0.3558 (4) | 0.0466 (13) | |
H5 | −0.1455 | −0.2325 | 0.4268 | 0.056* | |
C6 | −0.2112 (4) | −0.3190 (7) | 0.2765 (4) | 0.0485 (13) | |
H6 | −0.2664 | −0.3876 | 0.2931 | 0.058* | |
C7 | −0.2036 (4) | −0.3118 (6) | 0.1727 (4) | 0.0479 (14) | |
H7 | −0.2526 | −0.3773 | 0.1189 | 0.058* | |
C8 | −0.2531 (4) | −0.1743 (5) | −0.0763 (4) | 0.0377 (12) | |
C9 | −0.3384 (4) | −0.1065 (7) | −0.0432 (4) | 0.0533 (14) | |
H9 | −0.3254 | −0.0718 | 0.0289 | 0.064* | |
C10 | −0.4453 (5) | −0.0874 (7) | −0.1145 (4) | 0.0659 (17) | |
H10 | −0.5042 | −0.0402 | −0.0907 | 0.079* | |
C11 | −0.4641 (5) | −0.1373 (7) | −0.2190 (5) | 0.0574 (15) | |
H11 | −0.5363 | −0.1259 | −0.2674 | 0.069* | |
C12 | −0.3795 (6) | −0.2026 (7) | −0.2529 (5) | 0.0620 (16) | |
H12 | −0.3925 | −0.2372 | −0.3250 | 0.074* | |
C13 | −0.2737 (5) | −0.2192 (7) | −0.1825 (4) | 0.0541 (15) | |
H13 | −0.2145 | −0.2620 | −0.2078 | 0.065* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0407 (5) | 0.0235 (4) | 0.0315 (5) | 0.000 | 0.0235 (3) | 0.000 |
Cl | 0.0486 (9) | 0.0256 (6) | 0.0435 (8) | 0.0021 (6) | 0.0286 (7) | −0.0019 (5) |
P | 0.0414 (9) | 0.0268 (6) | 0.0384 (8) | −0.0027 (6) | 0.0245 (7) | −0.0014 (6) |
C1 | 0.084 (4) | 0.020 (2) | 0.067 (4) | 0.001 (2) | 0.050 (4) | 0.000 (2) |
C2 | 0.035 (3) | 0.034 (2) | 0.037 (3) | 0.008 (2) | 0.020 (2) | 0.010 (2) |
C3 | 0.042 (3) | 0.042 (3) | 0.035 (3) | −0.004 (2) | 0.018 (2) | 0.007 (2) |
C4 | 0.050 (3) | 0.049 (3) | 0.042 (3) | 0.003 (3) | 0.017 (3) | 0.007 (2) |
C5 | 0.052 (3) | 0.058 (3) | 0.036 (3) | 0.008 (3) | 0.023 (3) | 0.008 (3) |
C6 | 0.046 (3) | 0.064 (3) | 0.042 (3) | −0.009 (3) | 0.024 (3) | 0.011 (3) |
C7 | 0.042 (3) | 0.062 (3) | 0.046 (3) | −0.009 (3) | 0.022 (3) | 0.006 (3) |
C8 | 0.047 (3) | 0.036 (3) | 0.034 (3) | −0.010 (2) | 0.019 (2) | −0.0011 (19) |
C9 | 0.049 (3) | 0.070 (4) | 0.039 (3) | 0.015 (3) | 0.008 (3) | −0.016 (3) |
C10 | 0.061 (4) | 0.092 (4) | 0.043 (4) | 0.013 (3) | 0.011 (3) | −0.010 (3) |
C11 | 0.059 (4) | 0.073 (4) | 0.035 (3) | −0.012 (3) | 0.003 (3) | 0.006 (3) |
C12 | 0.073 (5) | 0.084 (4) | 0.029 (3) | −0.026 (3) | 0.014 (3) | −0.002 (3) |
C13 | 0.062 (4) | 0.067 (4) | 0.042 (3) | −0.014 (3) | 0.029 (3) | −0.019 (3) |
Ni—P | 2.1346 (13) | C5—C6 | 1.373 (7) |
Ni—Pi | 2.1346 (13) | C5—H5 | 0.9500 |
Ni—Cli | 2.2054 (13) | C6—C7 | 1.384 (7) |
Ni—Cl | 2.2054 (13) | C6—H6 | 0.9500 |
P—C2 | 1.800 (4) | C7—H7 | 0.9500 |
P—C8 | 1.804 (5) | C8—C9 | 1.364 (7) |
P—C1 | 1.836 (4) | C8—C13 | 1.384 (7) |
C1—C1i | 1.413 (10) | C9—C10 | 1.407 (8) |
C1—H1A | 0.9900 | C9—H9 | 0.9500 |
C1—H1B | 0.9900 | C10—C11 | 1.376 (7) |
C2—C7 | 1.383 (6) | C10—H10 | 0.9500 |
C2—C3 | 1.392 (6) | C11—C12 | 1.354 (8) |
C3—C4 | 1.381 (7) | C11—H11 | 0.9500 |
C3—H3 | 0.9500 | C12—C13 | 1.388 (8) |
C4—C5 | 1.366 (7) | C12—H12 | 0.9500 |
C4—H4 | 0.9500 | C13—H13 | 0.9500 |
P—Ni—Pi | 87.18 (7) | C4—C5—C6 | 119.5 (5) |
P—Ni—Cli | 173.87 (6) | C4—C5—H5 | 120.3 |
Pi—Ni—Cli | 87.78 (4) | C6—C5—H5 | 120.3 |
P—Ni—Cl | 87.78 (4) | C5—C6—C7 | 120.5 (5) |
Pi—Ni—Cl | 173.87 (6) | C5—C6—H6 | 119.7 |
Cli—Ni—Cl | 97.45 (7) | C7—C6—H6 | 119.7 |
C2—P—C8 | 108.1 (2) | C2—C7—C6 | 120.6 (5) |
C2—P—C1 | 105.9 (2) | C2—C7—H7 | 119.7 |
C8—P—C1 | 106.0 (2) | C6—C7—H7 | 119.7 |
C2—P—Ni | 111.42 (17) | C9—C8—C13 | 118.2 (5) |
C8—P—Ni | 116.05 (15) | C9—C8—P | 121.4 (4) |
C1—P—Ni | 108.77 (16) | C13—C8—P | 120.2 (4) |
C1i—C1—P | 109.9 (3) | C8—C9—C10 | 120.8 (5) |
C1i—C1—H1A | 109.7 | C8—C9—H9 | 119.6 |
P—C1—H1A | 109.7 | C10—C9—H9 | 119.6 |
C1i—C1—H1B | 109.7 | C11—C10—C9 | 119.7 (6) |
P—C1—H1B | 109.7 | C11—C10—H10 | 120.2 |
H1A—C1—H1B | 108.2 | C9—C10—H10 | 120.2 |
C7—C2—C3 | 118.1 (4) | C12—C11—C10 | 119.9 (5) |
C7—C2—P | 122.6 (4) | C12—C11—H11 | 120.0 |
C3—C2—P | 119.3 (3) | C10—C11—H11 | 120.0 |
C4—C3—C2 | 120.7 (4) | C11—C12—C13 | 120.2 (5) |
C4—C3—H3 | 119.6 | C11—C12—H12 | 119.9 |
C2—C3—H3 | 119.6 | C13—C12—H12 | 119.9 |
C5—C4—C3 | 120.5 (5) | C8—C13—C12 | 121.1 (5) |
C5—C4—H4 | 119.7 | C8—C13—H13 | 119.4 |
C3—C4—H4 | 119.7 | C12—C13—H13 | 119.4 |
Pi—Ni—P—C2 | 106.36 (17) | C4—C5—C6—C7 | −0.5 (8) |
Cl—Ni—P—C2 | −70.14 (15) | C3—C2—C7—C6 | 2.6 (7) |
Pi—Ni—P—C8 | −129.38 (19) | P—C2—C7—C6 | −178.3 (4) |
Cl—Ni—P—C8 | 54.11 (17) | C5—C6—C7—C2 | −1.4 (7) |
Pi—Ni—P—C1 | −10.0 (2) | C2—P—C8—C9 | 28.5 (5) |
Cl—Ni—P—C1 | 173.5 (2) | C1—P—C8—C9 | 141.7 (4) |
C2—P—C1—C1i | −85.2 (5) | Ni—P—C8—C9 | −97.4 (4) |
C8—P—C1—C1i | 160.1 (5) | C2—P—C8—C13 | −156.2 (4) |
Ni—P—C1—C1i | 34.6 (5) | C1—P—C8—C13 | −43.0 (4) |
C8—P—C2—C7 | 43.2 (4) | Ni—P—C8—C13 | 77.8 (4) |
C1—P—C2—C7 | −70.0 (4) | C13—C8—C9—C10 | 1.8 (8) |
Ni—P—C2—C7 | 171.9 (3) | P—C8—C9—C10 | 177.2 (4) |
C8—P—C2—C3 | −137.6 (4) | C8—C9—C10—C11 | −0.1 (9) |
C1—P—C2—C3 | 109.1 (4) | C9—C10—C11—C12 | −0.7 (9) |
Ni—P—C2—C3 | −9.0 (4) | C10—C11—C12—C13 | −0.1 (9) |
C7—C2—C3—C4 | −2.0 (7) | C9—C8—C13—C12 | −2.7 (8) |
P—C2—C3—C4 | 178.8 (4) | P—C8—C13—C12 | −178.1 (4) |
C2—C3—C4—C5 | 0.3 (7) | C11—C12—C13—C8 | 1.9 (8) |
C3—C4—C5—C6 | 1.0 (8) | P—C1—C1i—Pi | −42.7 (6) |
Symmetry code: (i) −x, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Clii | 0.99 | 2.69 | 3.556 (4) | 147 |
C12—H12···Cliii | 0.95 | 2.74 | 3.664 (6) | 166 |
Symmetry codes: (ii) x, y−1, z; (iii) −x−1/2, y−1/2, −z−1/2. |
[NiCl2(C26H24P2)] | F(000) = 544 |
Mr = 528.0 | Dx = 1.379 Mg m−3 |
Monoclinic, I2 | Mo Kα radiation, λ = 0.71073 Å |
a = 12.5688 (15) Å | Cell parameters from 4976 reflections |
b = 8.0208 (8) Å | θ = 3.0–30.1° |
c = 13.0871 (9) Å | µ = 1.11 mm−1 |
β = 105.531 (4)° | T = 293 K |
V = 1271.2 (2) Å3 | Needle, brown yellow |
Z = 2 | 0.35 × 0.07 × 0.05 mm |
Kappa-CCD diffractometer | 2861 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 1576 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.050 |
Detector resolution: 9.091 pixels mm-1 | θmax = 30.1°, θmin = 3.0° |
ϕ and ω scans | h = −16→13 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −10→8 |
Tmin = 0.896, Tmax = 0.955 | l = −15→16 |
4976 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.100 | w = 1/[σ2(Fo2) + (0.0223P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.95 | (Δ/σ)max < 0.001 |
2861 reflections | Δρmax = 0.27 e Å−3 |
141 parameters | Δρmin = −0.34 e Å−3 |
1 restraint | Absolute structure: (Flack, 1983) |
Primary atom site location: heavy-atom method | Absolute structure parameter: 0.01 (2) |
[NiCl2(C26H24P2)] | V = 1271.2 (2) Å3 |
Mr = 528.0 | Z = 2 |
Monoclinic, I2 | Mo Kα radiation |
a = 12.5688 (15) Å | µ = 1.11 mm−1 |
b = 8.0208 (8) Å | T = 293 K |
c = 13.0871 (9) Å | 0.35 × 0.07 × 0.05 mm |
β = 105.531 (4)° |
Kappa-CCD diffractometer | 2861 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 1576 reflections with I > 2σ(I) |
Tmin = 0.896, Tmax = 0.955 | Rint = 0.050 |
4976 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.100 | Δρmax = 0.27 e Å−3 |
S = 0.95 | Δρmin = −0.34 e Å−3 |
2861 reflections | Absolute structure: (Flack, 1983) |
141 parameters | Absolute structure parameter: 0.01 (2) |
1 restraint |
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 placed in claculated positions and refined with a riding model. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.0000 | −0.00204 (12) | 0.0000 | 0.0450 (2) | |
Cl | −0.12129 (14) | −0.18466 (10) | 0.02479 (13) | 0.0599 (5) | |
P | −0.11247 (15) | 0.19034 (13) | 0.01417 (13) | 0.0512 (5) | |
C1 | −0.0578 (4) | 0.3909 (5) | −0.0161 (6) | 0.085 (2) | |
H1A | −0.0856 | 0.4796 | 0.0201 | 0.102* | |
H1B | −0.0829 | 0.4118 | −0.0917 | 0.102* | |
C2 | −0.1245 (4) | 0.2097 (6) | 0.1476 (4) | 0.0530 (13) | |
C3 | −0.0545 (5) | 0.1204 (7) | 0.2277 (5) | 0.0670 (15) | |
H3 | −0.0013 | 0.0517 | 0.2121 | 0.080* | |
C4 | −0.0619 (5) | 0.1312 (8) | 0.3301 (5) | 0.0811 (18) | |
H4 | −0.0140 | 0.0692 | 0.3829 | 0.097* | |
C5 | −0.1385 (6) | 0.2317 (8) | 0.3556 (5) | 0.0870 (19) | |
H5 | −0.1435 | 0.2392 | 0.4250 | 0.104* | |
C6 | −0.2073 (5) | 0.3206 (9) | 0.2766 (5) | 0.091 (2) | |
H6 | −0.2606 | 0.3886 | 0.2924 | 0.109* | |
C7 | −0.1999 (5) | 0.3126 (7) | 0.1746 (5) | 0.0770 (18) | |
H7 | −0.2466 | 0.3776 | 0.1227 | 0.092* | |
C8 | −0.2490 (5) | 0.1755 (6) | −0.0730 (4) | 0.0589 (15) | |
C9 | −0.3342 (5) | 0.1083 (8) | −0.0431 (5) | 0.088 (2) | |
H9 | −0.3226 | 0.0694 | 0.0260 | 0.105* | |
C10 | −0.4392 (7) | 0.0956 (9) | −0.1126 (7) | 0.119 (3) | |
H10 | −0.4971 | 0.0546 | −0.0882 | 0.143* | |
C11 | −0.4581 (7) | 0.1420 (9) | −0.2153 (7) | 0.107 (2) | |
H11 | −0.5276 | 0.1296 | −0.2626 | 0.129* | |
C12 | −0.3729 (8) | 0.2070 (10) | −0.2474 (6) | 0.107 (3) | |
H12 | −0.3847 | 0.2413 | −0.3174 | 0.128* | |
C13 | −0.2686 (6) | 0.2237 (8) | −0.1785 (6) | 0.094 (2) | |
H13 | −0.2114 | 0.2675 | −0.2029 | 0.112* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0650 (5) | 0.0320 (4) | 0.0479 (5) | 0.000 | 0.0325 (4) | 0.000 |
Cl | 0.0807 (12) | 0.0392 (9) | 0.0738 (12) | −0.0059 (7) | 0.0450 (10) | 0.0022 (7) |
P | 0.0683 (12) | 0.0386 (8) | 0.0574 (11) | 0.0049 (7) | 0.0352 (10) | 0.0008 (7) |
C1 | 0.127 (6) | 0.031 (3) | 0.122 (6) | 0.005 (3) | 0.076 (6) | 0.000 (3) |
C2 | 0.058 (3) | 0.060 (3) | 0.047 (3) | 0.001 (3) | 0.024 (3) | −0.012 (3) |
C3 | 0.078 (4) | 0.067 (3) | 0.065 (4) | 0.006 (3) | 0.033 (4) | −0.012 (3) |
C4 | 0.098 (5) | 0.095 (4) | 0.053 (4) | 0.001 (4) | 0.024 (4) | −0.011 (3) |
C5 | 0.108 (6) | 0.108 (5) | 0.055 (4) | −0.013 (4) | 0.039 (4) | −0.026 (4) |
C6 | 0.083 (5) | 0.130 (6) | 0.064 (5) | 0.026 (4) | 0.029 (4) | −0.027 (4) |
C7 | 0.073 (4) | 0.098 (5) | 0.065 (4) | 0.023 (3) | 0.028 (3) | −0.012 (3) |
C8 | 0.068 (4) | 0.069 (4) | 0.043 (4) | 0.017 (3) | 0.021 (3) | 0.010 (2) |
C9 | 0.071 (5) | 0.115 (5) | 0.066 (5) | −0.027 (4) | −0.002 (4) | 0.025 (4) |
C10 | 0.099 (6) | 0.164 (7) | 0.077 (6) | −0.019 (5) | −0.004 (5) | 0.017 (5) |
C11 | 0.109 (7) | 0.125 (6) | 0.079 (6) | 0.022 (5) | 0.007 (5) | −0.012 (5) |
C12 | 0.132 (8) | 0.130 (6) | 0.054 (5) | 0.047 (6) | 0.020 (6) | 0.012 (4) |
C13 | 0.097 (6) | 0.122 (5) | 0.072 (5) | 0.028 (4) | 0.041 (5) | 0.033 (4) |
Ni—Pi | 2.1340 (15) | C5—C6 | 1.358 (8) |
Ni—P | 2.1340 (15) | C5—H5 | 0.9300 |
Ni—Cl | 2.1999 (14) | C6—C7 | 1.364 (8) |
Ni—Cli | 2.1999 (14) | C6—H6 | 0.9300 |
P—C8 | 1.792 (6) | C7—H7 | 0.9300 |
P—C2 | 1.800 (5) | C8—C9 | 1.348 (7) |
P—C1 | 1.833 (4) | C8—C13 | 1.390 (7) |
C1—C1i | 1.400 (11) | C9—C10 | 1.392 (9) |
C1—H1A | 0.9700 | C9—H9 | 0.9300 |
C1—H1B | 0.9700 | C10—C11 | 1.353 (9) |
C2—C7 | 1.372 (6) | C10—H10 | 0.9300 |
C2—C3 | 1.375 (7) | C11—C12 | 1.355 (9) |
C3—C4 | 1.371 (7) | C11—H11 | 0.9300 |
C3—H3 | 0.9300 | C12—C13 | 1.384 (9) |
C4—C5 | 1.364 (7) | C12—H12 | 0.9300 |
C4—H4 | 0.9300 | C13—H13 | 0.9300 |
Pi—Ni—P | 87.38 (8) | C6—C5—C4 | 118.1 (6) |
Pi—Ni—Cl | 174.60 (7) | C6—C5—H5 | 121.0 |
P—Ni—Cl | 88.13 (4) | C4—C5—H5 | 121.0 |
Pi—Ni—Cli | 88.13 (4) | C5—C6—C7 | 121.6 (6) |
P—Ni—Cli | 174.60 (7) | C5—C6—H6 | 119.2 |
Cl—Ni—Cli | 96.51 (8) | C7—C6—H6 | 119.2 |
C8—P—C2 | 108.0 (2) | C6—C7—C2 | 120.8 (6) |
C8—P—C1 | 105.7 (3) | C6—C7—H7 | 119.6 |
C2—P—C1 | 105.5 (3) | C2—C7—H7 | 119.6 |
C8—P—Ni | 116.12 (16) | C9—C8—C13 | 117.1 (6) |
C2—P—Ni | 112.12 (19) | C9—C8—P | 122.8 (4) |
C1—P—Ni | 108.68 (15) | C13—C8—P | 119.9 (5) |
C1i—C1—P | 110.7 (3) | C8—C9—C10 | 121.8 (6) |
C1i—C1—H1A | 109.5 | C8—C9—H9 | 119.1 |
P—C1—H1A | 109.5 | C10—C9—H9 | 119.1 |
C1i—C1—H1B | 109.5 | C11—C10—C9 | 120.9 (7) |
P—C1—H1B | 109.5 | C11—C10—H10 | 119.6 |
H1A—C1—H1B | 108.1 | C9—C10—H10 | 119.6 |
C7—C2—C3 | 117.6 (5) | C10—C11—C12 | 118.0 (8) |
C7—C2—P | 123.0 (4) | C10—C11—H11 | 121.0 |
C3—C2—P | 119.4 (4) | C12—C11—H11 | 121.0 |
C4—C3—C2 | 121.0 (5) | C11—C12—C13 | 121.7 (7) |
C4—C3—H3 | 119.5 | C11—C12—H12 | 119.2 |
C2—C3—H3 | 119.5 | C13—C12—H12 | 119.2 |
C5—C4—C3 | 120.9 (6) | C12—C13—C8 | 120.4 (6) |
C5—C4—H4 | 119.5 | C12—C13—H13 | 119.8 |
C3—C4—H4 | 119.5 | C8—C13—H13 | 119.8 |
Pi—Ni—P—C8 | 128.3 (2) | C4—C5—C6—C7 | −0.9 (11) |
Cl—Ni—P—C8 | −54.67 (19) | C5—C6—C7—C2 | 2.0 (10) |
Pi—Ni—P—C2 | −106.9 (2) | C3—C2—C7—C6 | −2.3 (8) |
Cl—Ni—P—C2 | 70.10 (18) | P—C2—C7—C6 | 178.8 (5) |
Pi—Ni—P—C1 | 9.4 (2) | C2—P—C8—C9 | −29.7 (6) |
Cl—Ni—P—C1 | −173.6 (3) | C1—P—C8—C9 | −142.2 (5) |
C8—P—C1—C1i | −158.0 (6) | Ni—P—C8—C9 | 97.2 (5) |
C2—P—C1—C1i | 87.7 (6) | C2—P—C8—C13 | 154.9 (4) |
Ni—P—C1—C1i | −32.7 (7) | C1—P—C8—C13 | 42.4 (5) |
C8—P—C2—C7 | −44.0 (5) | Ni—P—C8—C13 | −78.2 (4) |
C1—P—C2—C7 | 68.7 (5) | C13—C8—C9—C10 | −3.4 (10) |
Ni—P—C2—C7 | −173.1 (4) | P—C8—C9—C10 | −178.9 (5) |
C8—P—C2—C3 | 137.1 (4) | C8—C9—C10—C11 | 3.8 (12) |
C1—P—C2—C3 | −110.2 (5) | C9—C10—C11—C12 | −2.5 (12) |
Ni—P—C2—C3 | 8.0 (5) | C10—C11—C12—C13 | 1.1 (12) |
C7—C2—C3—C4 | 1.5 (8) | C11—C12—C13—C8 | −0.9 (11) |
P—C2—C3—C4 | −179.5 (4) | C9—C8—C13—C12 | 2.0 (9) |
C2—C3—C4—C5 | −0.4 (9) | P—C8—C13—C12 | 177.6 (5) |
C3—C4—C5—C6 | 0.0 (10) | P—C1—C1i—Pi | 40.6 (8) |
Symmetry code: (i) −x, y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Clii | 0.97 | 2.73 | 3.570 (4) | 145 |
C12—H12···Cliii | 0.93 | 2.80 | 3.714 (8) | 168 |
Symmetry codes: (ii) x, y+1, z; (iii) −x−1/2, y+1/2, −z−1/2. |
[NiCl2(C26H24P2)] | F(000) = 1088 |
Mr = 528.0 | Dx = 1.486 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 11.2779 (3) Å | Cell parameters from 20644 reflections |
b = 13.3386 (4) Å | θ = 2.9–27.5° |
c = 15.8739 (5) Å | µ = 1.20 mm−1 |
β = 98.7953 (16)° | T = 150 K |
V = 2359.85 (12) Å3 | Block, brown yellow |
Z = 4 | 0.20 × 0.15 × 0.10 mm |
Kappa-CCD diffractometer | 5198 independent reflections |
Radiation source: Enraf Nonius FR591 rotating anode | 4070 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.042 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 2.9° |
ϕ and ω scans | h = −14→14 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | k = −16→17 |
Tmin = 0.706, Tmax = 0.950 | l = −17→20 |
9650 measured reflections |
Refinement on F2 | Primary atom site location: heavy-atom method |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.042 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0671P)2 + 0.0545P] where P = (Fo2 + 2Fc2)/3 |
5198 reflections | (Δ/σ)max < 0.001 |
280 parameters | Δρmax = 0.71 e Å−3 |
0 restraints | Δρmin = −0.54 e Å−3 |
[NiCl2(C26H24P2)] | V = 2359.85 (12) Å3 |
Mr = 528.0 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.2779 (3) Å | µ = 1.20 mm−1 |
b = 13.3386 (4) Å | T = 150 K |
c = 15.8739 (5) Å | 0.20 × 0.15 × 0.10 mm |
β = 98.7953 (16)° |
Kappa-CCD diffractometer | 5198 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995, 1997) | 4070 reflections with I > 2σ(I) |
Tmin = 0.706, Tmax = 0.950 | Rint = 0.042 |
9650 measured reflections |
R[F2 > 2σ(F2)] = 0.042 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.71 e Å−3 |
5198 reflections | Δρmin = −0.54 e Å−3 |
280 parameters |
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 placed in calculated positions and refined with a riding model. |
x | y | z | Uiso*/Ueq | ||
Ni | 0.12587 (3) | 0.22015 (2) | 0.205630 (17) | 0.02078 (11) | |
Cl1 | 0.00827 (6) | 0.26607 (5) | 0.29716 (4) | 0.03211 (17) | |
Cl2 | 0.28647 (6) | 0.20315 (5) | 0.30257 (4) | 0.03251 (17) | |
P1 | −0.02871 (6) | 0.21138 (4) | 0.10837 (4) | 0.01938 (16) | |
P2 | 0.23140 (6) | 0.18286 (5) | 0.10808 (4) | 0.02161 (16) | |
C1 | 0.0152 (2) | 0.14116 (18) | 0.01856 (14) | 0.0243 (5) | |
H1A | 0.0218 | 0.0688 | 0.0322 | 0.029* | |
H1B | −0.0452 | 0.1502 | −0.0331 | 0.029* | |
C2 | 0.1355 (2) | 0.18237 (19) | 0.00392 (14) | 0.0242 (5) | |
H2A | 0.1263 | 0.2512 | −0.0195 | 0.029* | |
H2B | 0.1708 | 0.1395 | −0.0367 | 0.029* | |
C3 | −0.1398 (2) | 0.33733 (19) | −0.01982 (16) | 0.0326 (6) | |
H3 | −0.1462 | 0.2795 | −0.0551 | 0.039* | |
C4 | −0.1845 (3) | 0.4287 (2) | −0.05265 (18) | 0.0414 (7) | |
H4 | −0.2208 | 0.4334 | −0.1106 | 0.050* | |
C5 | −0.1761 (2) | 0.5120 (2) | −0.00163 (19) | 0.0372 (7) | |
H5 | −0.2081 | 0.5740 | −0.0242 | 0.045* | |
C6 | −0.1221 (3) | 0.5067 (2) | 0.08139 (19) | 0.0387 (7) | |
H6 | −0.1161 | 0.5650 | 0.1162 | 0.046* | |
C7 | −0.0760 (2) | 0.41594 (18) | 0.11475 (17) | 0.0321 (6) | |
H7 | −0.0375 | 0.4124 | 0.1722 | 0.039* | |
C8 | −0.0860 (2) | 0.33079 (17) | 0.06458 (15) | 0.0223 (5) | |
C9 | −0.2623 (2) | 0.1870 (2) | 0.14406 (16) | 0.0305 (6) | |
H9 | −0.2738 | 0.2561 | 0.1307 | 0.037* | |
C10 | −0.3546 (3) | 0.1312 (2) | 0.16905 (18) | 0.0381 (7) | |
H10 | −0.4295 | 0.1622 | 0.1727 | 0.046* | |
C11 | −0.3384 (3) | 0.0307 (2) | 0.18870 (18) | 0.0381 (7) | |
H11 | −0.4023 | −0.0072 | 0.2053 | 0.046* | |
C12 | −0.2296 (3) | −0.0145 (2) | 0.18430 (17) | 0.0348 (6) | |
H12 | −0.2188 | −0.0837 | 0.1976 | 0.042* | |
C13 | −0.1368 (2) | 0.04049 (18) | 0.16066 (16) | 0.0290 (6) | |
H13 | −0.0612 | 0.0095 | 0.1593 | 0.035* | |
C14 | −0.1527 (2) | 0.14153 (17) | 0.13868 (14) | 0.0220 (5) | |
C15 | 0.4070 (2) | 0.33062 (19) | 0.15635 (17) | 0.0310 (6) | |
H15 | 0.3801 | 0.3308 | 0.2102 | 0.037* | |
C16 | 0.4969 (2) | 0.3955 (2) | 0.14067 (18) | 0.0367 (7) | |
H16 | 0.5323 | 0.4396 | 0.1844 | 0.044* | |
C17 | 0.5354 (2) | 0.3970 (2) | 0.06276 (18) | 0.0361 (7) | |
H17 | 0.5975 | 0.4416 | 0.0529 | 0.043* | |
C18 | 0.4841 (2) | 0.3338 (2) | −0.00121 (17) | 0.0345 (6) | |
H18 | 0.5105 | 0.3349 | −0.0552 | 0.041* | |
C19 | 0.3937 (2) | 0.26838 (19) | 0.01345 (16) | 0.0289 (6) | |
H19 | 0.3574 | 0.2258 | −0.0311 | 0.035* | |
C20 | 0.3558 (2) | 0.26465 (18) | 0.09234 (15) | 0.0247 (5) | |
C21 | 0.2416 (2) | −0.0095 (2) | 0.17806 (17) | 0.0315 (6) | |
H21 | 0.1925 | 0.0172 | 0.2163 | 0.038* | |
C22 | 0.2717 (3) | −0.1096 (2) | 0.18212 (17) | 0.0359 (7) | |
H22 | 0.2427 | −0.1518 | 0.2227 | 0.043* | |
C23 | 0.3436 (3) | −0.1487 (2) | 0.12780 (18) | 0.0372 (7) | |
H23 | 0.3664 | −0.2173 | 0.1322 | 0.045* | |
C24 | 0.3825 (3) | −0.0890 (2) | 0.06739 (19) | 0.0406 (7) | |
H24 | 0.4301 | −0.1167 | 0.0287 | 0.049* | |
C25 | 0.3525 (2) | 0.01224 (19) | 0.06254 (17) | 0.0334 (6) | |
H25 | 0.3802 | 0.0535 | 0.0208 | 0.040* | |
C26 | 0.2825 (2) | 0.05310 (18) | 0.11831 (14) | 0.0237 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Ni | 0.0267 (2) | 0.01972 (19) | 0.01563 (18) | 0.00147 (12) | 0.00224 (13) | −0.00248 (12) |
Cl1 | 0.0376 (4) | 0.0391 (4) | 0.0209 (3) | 0.0012 (3) | 0.0082 (3) | −0.0078 (3) |
Cl2 | 0.0364 (4) | 0.0371 (4) | 0.0216 (3) | 0.0029 (3) | −0.0033 (3) | 0.0010 (3) |
P1 | 0.0255 (4) | 0.0141 (3) | 0.0183 (3) | 0.0019 (2) | 0.0026 (3) | −0.0016 (2) |
P2 | 0.0266 (3) | 0.0201 (3) | 0.0180 (3) | 0.0041 (3) | 0.0029 (2) | −0.0003 (3) |
C1 | 0.0349 (14) | 0.0170 (12) | 0.0199 (11) | 0.0033 (10) | 0.0011 (10) | −0.0046 (10) |
C2 | 0.0320 (14) | 0.0234 (13) | 0.0174 (11) | 0.0083 (11) | 0.0041 (10) | −0.0025 (10) |
C3 | 0.0409 (16) | 0.0228 (13) | 0.0322 (14) | 0.0019 (12) | −0.0007 (12) | 0.0011 (11) |
C4 | 0.0484 (19) | 0.0334 (16) | 0.0390 (16) | 0.0042 (14) | −0.0038 (14) | 0.0115 (13) |
C5 | 0.0358 (16) | 0.0212 (13) | 0.0564 (18) | 0.0063 (12) | 0.0125 (14) | 0.0154 (13) |
C6 | 0.0531 (19) | 0.0176 (13) | 0.0484 (18) | 0.0049 (12) | 0.0175 (14) | −0.0021 (13) |
C7 | 0.0455 (17) | 0.0219 (13) | 0.0298 (14) | 0.0024 (12) | 0.0081 (12) | −0.0023 (11) |
C8 | 0.0256 (13) | 0.0146 (11) | 0.0280 (13) | 0.0027 (9) | 0.0078 (10) | 0.0041 (10) |
C9 | 0.0332 (15) | 0.0249 (13) | 0.0329 (14) | 0.0049 (11) | 0.0029 (11) | 0.0065 (11) |
C10 | 0.0283 (15) | 0.0367 (16) | 0.0498 (17) | 0.0036 (12) | 0.0070 (13) | 0.0082 (14) |
C11 | 0.0328 (16) | 0.0364 (16) | 0.0454 (16) | −0.0082 (13) | 0.0072 (13) | 0.0131 (13) |
C12 | 0.0466 (18) | 0.0212 (13) | 0.0373 (15) | −0.0031 (12) | 0.0086 (13) | 0.0096 (12) |
C13 | 0.0303 (14) | 0.0214 (13) | 0.0353 (14) | 0.0040 (11) | 0.0056 (11) | 0.0027 (11) |
C14 | 0.0276 (13) | 0.0189 (12) | 0.0189 (11) | −0.0016 (10) | 0.0019 (10) | 0.0004 (10) |
C15 | 0.0358 (15) | 0.0279 (14) | 0.0301 (14) | 0.0014 (12) | 0.0071 (11) | −0.0037 (11) |
C16 | 0.0350 (16) | 0.0341 (16) | 0.0405 (16) | −0.0020 (13) | 0.0037 (13) | −0.0013 (13) |
C17 | 0.0290 (15) | 0.0293 (15) | 0.0507 (17) | 0.0024 (12) | 0.0083 (13) | 0.0101 (13) |
C18 | 0.0391 (16) | 0.0310 (15) | 0.0356 (15) | 0.0052 (13) | 0.0134 (12) | 0.0090 (13) |
C19 | 0.0325 (15) | 0.0266 (14) | 0.0280 (14) | 0.0055 (11) | 0.0055 (11) | 0.0028 (11) |
C20 | 0.0253 (13) | 0.0221 (13) | 0.0263 (13) | 0.0060 (10) | 0.0032 (10) | 0.0025 (10) |
C21 | 0.0382 (16) | 0.0285 (14) | 0.0289 (13) | 0.0054 (12) | 0.0091 (11) | 0.0025 (12) |
C22 | 0.0449 (17) | 0.0292 (15) | 0.0334 (14) | −0.0003 (13) | 0.0054 (13) | 0.0099 (12) |
C23 | 0.0429 (17) | 0.0180 (13) | 0.0491 (17) | 0.0033 (12) | 0.0018 (14) | −0.0026 (12) |
C24 | 0.0450 (18) | 0.0280 (15) | 0.0524 (18) | 0.0078 (13) | 0.0196 (15) | −0.0082 (14) |
C25 | 0.0345 (15) | 0.0259 (14) | 0.0430 (16) | −0.0012 (12) | 0.0163 (13) | 0.0007 (12) |
C26 | 0.0272 (13) | 0.0195 (12) | 0.0237 (12) | 0.0041 (10) | 0.0014 (10) | 0.0001 (10) |
Ni—P1 | 2.1479 (7) | C10—H10 | 0.9500 |
Ni—P2 | 2.1507 (7) | C11—C12 | 1.378 (4) |
Ni—Cl1 | 2.1987 (7) | C11—H11 | 0.9500 |
Ni—Cl2 | 2.2017 (7) | C12—C13 | 1.377 (4) |
P1—C14 | 1.806 (2) | C12—H12 | 0.9500 |
P1—C8 | 1.817 (2) | C13—C14 | 1.397 (3) |
P1—C1 | 1.836 (2) | C13—H13 | 0.9500 |
P2—C26 | 1.824 (2) | C15—C16 | 1.384 (4) |
P2—C20 | 1.824 (3) | C15—C20 | 1.400 (4) |
P2—C2 | 1.832 (2) | C15—H15 | 0.9500 |
C1—C2 | 1.515 (3) | C16—C17 | 1.372 (4) |
C1—H1A | 0.9900 | C16—H16 | 0.9500 |
C1—H1B | 0.9900 | C17—C18 | 1.377 (4) |
C2—H2A | 0.9900 | C17—H17 | 0.9500 |
C2—H2B | 0.9900 | C18—C19 | 1.388 (4) |
C3—C8 | 1.387 (3) | C18—H18 | 0.9500 |
C3—C4 | 1.389 (4) | C19—C20 | 1.384 (4) |
C3—H3 | 0.9500 | C19—H19 | 0.9500 |
C4—C5 | 1.370 (4) | C21—C22 | 1.377 (4) |
C4—H4 | 0.9500 | C21—C26 | 1.394 (3) |
C5—C6 | 1.366 (4) | C21—H21 | 0.9500 |
C5—H5 | 0.9500 | C22—C23 | 1.374 (4) |
C6—C7 | 1.390 (4) | C22—H22 | 0.9500 |
C6—H6 | 0.9500 | C23—C24 | 1.369 (4) |
C7—C8 | 1.382 (3) | C23—H23 | 0.9500 |
C7—H7 | 0.9500 | C24—C25 | 1.391 (4) |
C9—C10 | 1.387 (4) | C24—H24 | 0.9500 |
C9—C14 | 1.390 (3) | C25—C26 | 1.385 (3) |
C9—H9 | 0.9500 | C25—H25 | 0.9500 |
C10—C11 | 1.381 (4) | ||
P1—Ni—P2 | 86.99 (2) | C11—C10—C9 | 120.4 (3) |
P1—Ni—Cl1 | 89.13 (3) | C11—C10—H10 | 119.8 |
P2—Ni—Cl1 | 175.09 (3) | C9—C10—H10 | 119.8 |
P1—Ni—Cl2 | 170.87 (3) | C12—C11—C10 | 120.1 (3) |
P2—Ni—Cl2 | 89.58 (3) | C12—C11—H11 | 119.9 |
Cl1—Ni—Cl2 | 94.69 (3) | C10—C11—H11 | 119.9 |
C14—P1—C8 | 108.04 (11) | C13—C12—C11 | 120.0 (2) |
C14—P1—C1 | 104.80 (11) | C13—C12—H12 | 120.0 |
C8—P1—C1 | 105.82 (11) | C11—C12—H12 | 120.0 |
C14—P1—Ni | 114.40 (8) | C12—C13—C14 | 120.5 (2) |
C8—P1—Ni | 115.43 (8) | C12—C13—H13 | 119.7 |
C1—P1—Ni | 107.48 (8) | C14—C13—H13 | 119.7 |
C26—P2—C20 | 109.92 (11) | C9—C14—C13 | 119.2 (2) |
C26—P2—C2 | 102.24 (11) | C9—C14—P1 | 121.53 (19) |
C20—P2—C2 | 103.81 (11) | C13—C14—P1 | 119.26 (19) |
C26—P2—Ni | 110.95 (8) | C16—C15—C20 | 119.6 (2) |
C20—P2—Ni | 118.82 (8) | C16—C15—H15 | 120.2 |
C2—P2—Ni | 109.59 (8) | C20—C15—H15 | 120.2 |
C2—C1—P1 | 106.75 (16) | C17—C16—C15 | 120.8 (3) |
C2—C1—H1A | 110.4 | C17—C16—H16 | 119.6 |
P1—C1—H1A | 110.4 | C15—C16—H16 | 119.6 |
C2—C1—H1B | 110.4 | C16—C17—C18 | 120.0 (3) |
P1—C1—H1B | 110.4 | C16—C17—H17 | 120.0 |
H1A—C1—H1B | 108.6 | C18—C17—H17 | 120.0 |
C1—C2—P2 | 106.37 (16) | C17—C18—C19 | 119.8 (2) |
C1—C2—H2A | 110.5 | C17—C18—H18 | 120.1 |
P2—C2—H2A | 110.5 | C19—C18—H18 | 120.1 |
C1—C2—H2B | 110.5 | C20—C19—C18 | 120.7 (3) |
P2—C2—H2B | 110.5 | C20—C19—H19 | 119.7 |
H2A—C2—H2B | 108.6 | C18—C19—H19 | 119.7 |
C8—C3—C4 | 119.9 (2) | C19—C20—C15 | 118.9 (2) |
C8—C3—H3 | 120.1 | C19—C20—P2 | 119.7 (2) |
C4—C3—H3 | 120.1 | C15—C20—P2 | 121.12 (19) |
C5—C4—C3 | 120.1 (3) | C22—C21—C26 | 120.5 (2) |
C5—C4—H4 | 119.9 | C22—C21—H21 | 119.8 |
C3—C4—H4 | 119.9 | C26—C21—H21 | 119.8 |
C6—C5—C4 | 120.5 (2) | C23—C22—C21 | 120.3 (3) |
C6—C5—H5 | 119.7 | C23—C22—H22 | 119.8 |
C4—C5—H5 | 119.7 | C21—C22—H22 | 119.8 |
C5—C6—C7 | 119.9 (3) | C24—C23—C22 | 120.1 (2) |
C5—C6—H6 | 120.1 | C24—C23—H23 | 120.0 |
C7—C6—H6 | 120.1 | C22—C23—H23 | 120.0 |
C8—C7—C6 | 120.2 (2) | C23—C24—C25 | 120.1 (3) |
C8—C7—H7 | 119.9 | C23—C24—H24 | 119.9 |
C6—C7—H7 | 119.9 | C25—C24—H24 | 119.9 |
C7—C8—C3 | 119.4 (2) | C26—C25—C24 | 120.3 (2) |
C7—C8—P1 | 120.48 (19) | C26—C25—H25 | 119.9 |
C3—C8—P1 | 120.16 (18) | C24—C25—H25 | 119.9 |
C10—C9—C14 | 119.8 (2) | C25—C26—C21 | 118.7 (2) |
C10—C9—H9 | 120.1 | C25—C26—P2 | 121.32 (19) |
C14—C9—H9 | 120.1 | C21—C26—P2 | 119.72 (18) |
P2—Ni—P1—C14 | 133.90 (9) | C10—C9—C14—P1 | −178.8 (2) |
Cl1—Ni—P1—C14 | −49.11 (9) | C12—C13—C14—C9 | 2.4 (4) |
P2—Ni—P1—C8 | −99.80 (9) | C12—C13—C14—P1 | 179.79 (19) |
Cl1—Ni—P1—C8 | 77.19 (9) | C8—P1—C14—C9 | −13.5 (2) |
P2—Ni—P1—C1 | 17.99 (9) | C1—P1—C14—C9 | −126.0 (2) |
Cl1—Ni—P1—C1 | −165.02 (9) | Ni—P1—C14—C9 | 116.57 (19) |
P1—Ni—P2—C26 | −105.03 (9) | C8—P1—C14—C13 | 169.21 (19) |
Cl2—Ni—P2—C26 | 66.50 (9) | C1—P1—C14—C13 | 56.7 (2) |
P1—Ni—P2—C20 | 126.14 (9) | Ni—P1—C14—C13 | −60.7 (2) |
Cl2—Ni—P2—C20 | −62.33 (9) | C20—C15—C16—C17 | 0.9 (4) |
P1—Ni—P2—C2 | 7.13 (9) | C15—C16—C17—C18 | 0.3 (4) |
Cl2—Ni—P2—C2 | 178.66 (9) | C16—C17—C18—C19 | −0.2 (4) |
C14—P1—C1—C2 | −167.27 (16) | C17—C18—C19—C20 | −1.2 (4) |
C8—P1—C1—C2 | 78.67 (18) | C18—C19—C20—C15 | 2.4 (4) |
Ni—P1—C1—C2 | −45.18 (17) | C18—C19—C20—P2 | 176.75 (19) |
P1—C1—C2—P2 | 49.90 (18) | C16—C15—C20—C19 | −2.2 (4) |
C26—P2—C2—C1 | 81.44 (17) | C16—C15—C20—P2 | −176.5 (2) |
C20—P2—C2—C1 | −164.21 (16) | C26—P2—C20—C19 | 76.5 (2) |
Ni—P2—C2—C1 | −36.30 (17) | C2—P2—C20—C19 | −32.3 (2) |
C8—C3—C4—C5 | −0.5 (4) | Ni—P2—C20—C19 | −154.24 (17) |
C3—C4—C5—C6 | 1.2 (4) | C26—P2—C20—C15 | −109.3 (2) |
C4—C5—C6—C7 | −0.5 (4) | C2—P2—C20—C15 | 142.0 (2) |
C5—C6—C7—C8 | −0.9 (4) | Ni—P2—C20—C15 | 20.0 (2) |
C6—C7—C8—C3 | 1.5 (4) | C26—C21—C22—C23 | 0.7 (4) |
C6—C7—C8—P1 | −178.7 (2) | C21—C22—C23—C24 | −2.1 (4) |
C4—C3—C8—C7 | −0.9 (4) | C22—C23—C24—C25 | 2.0 (5) |
C4—C3—C8—P1 | 179.4 (2) | C23—C24—C25—C26 | −0.5 (4) |
C14—P1—C8—C7 | 97.8 (2) | C24—C25—C26—C21 | −1.0 (4) |
C1—P1—C8—C7 | −150.4 (2) | C24—C25—C26—P2 | −174.9 (2) |
Ni—P1—C8—C7 | −31.7 (2) | C22—C21—C26—C25 | 0.9 (4) |
C14—P1—C8—C3 | −82.4 (2) | C22—C21—C26—P2 | 174.9 (2) |
C1—P1—C8—C3 | 29.4 (2) | C20—P2—C26—C25 | −46.3 (2) |
Ni—P1—C8—C3 | 148.08 (19) | C2—P2—C26—C25 | 63.5 (2) |
C14—C9—C10—C11 | 0.1 (4) | Ni—P2—C26—C25 | −179.76 (19) |
C9—C10—C11—C12 | 0.6 (4) | C20—P2—C26—C21 | 139.8 (2) |
C10—C11—C12—C13 | 0.3 (4) | C2—P2—C26—C21 | −110.4 (2) |
C11—C12—C13—C14 | −1.8 (4) | Ni—P2—C26—C21 | 6.4 (2) |
C10—C9—C14—C13 | −1.5 (4) |
Experimental details
C(150) | C(293) | A(150) | |
Crystal data | |||
Chemical formula | [NiCl2(C26H24P2)] | [NiCl2(C26H24P2)] | [NiCl2(C26H24P2)] |
Mr | 528.0 | 528.0 | 528.0 |
Crystal system, space group | Monoclinic, I2 | Monoclinic, I2 | Monoclinic, P21/c |
Temperature (K) | 150 | 293 | 150 |
a, b, c (Å) | 12.4551 (14), 7.9901 (8), 13.0350 (19) | 12.5688 (15), 8.0208 (8), 13.0871 (9) | 11.2779 (3), 13.3386 (4), 15.8739 (5) |
β (°) | 105.983 (5) | 105.531 (4) | 98.7953 (16) |
V (Å3) | 1247.1 (3) | 1271.2 (2) | 2359.85 (12) |
Z | 2 | 2 | 4 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 1.13 | 1.11 | 1.20 |
Crystal size (mm) | 0.20 × 0.03 × 0.03 | 0.35 × 0.07 × 0.05 | 0.20 × 0.15 × 0.10 |
Data collection | |||
Diffractometer | Kappa-CCD diffractometer | Kappa-CCD diffractometer | Kappa-CCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997) | Multi-scan (SORTAV; Blessing, 1995, 1997) |
Tmin, Tmax | 0.887, 0.999 | 0.896, 0.955 | 0.706, 0.950 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5686, 2686, 1946 | 4976, 2861, 1576 | 9650, 5198, 4070 |
Rint | 0.064 | 0.050 | 0.042 |
(sin θ/λ)max (Å−1) | 0.650 | 0.706 | 0.650 |
Refinement | |||
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.105, 1.04 | 0.049, 0.100, 0.95 | 0.042, 0.117, 1.06 |
No. of reflections | 2686 | 2861 | 5198 |
No. of parameters | 141 | 141 | 280 |
No. of restraints | 1 | 1 | 0 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.58 | 0.27, −0.34 | 0.71, −0.54 |
Absolute structure | (Flack, 1983) | (Flack, 1983) | ? |
Absolute structure parameter | 0.01 (2) | 0.01 (2) | ? |
Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS86 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Cli | 0.99 | 2.69 | 3.556 (4) | 147 |
C12—H12···Clii | 0.95 | 2.74 | 3.664 (6) | 166 |
Symmetry codes: (i) x, y−1, z; (ii) −x−1/2, y−1/2, −z−1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1A···Cli | 0.97 | 2.73 | 3.570 (4) | 145 |
C12—H12···Clii | 0.93 | 2.80 | 3.714 (8) | 168 |
Symmetry codes: (i) x, y+1, z; (ii) −x−1/2, y+1/2, −z−1/2. |
A | A' | A(150) | B | C(293) | C(150) | |
Ni—Cl | 2.199 (2) | 2.1990 (6) | 2.2002 (4) | 2.2003 (11) | 2.1999 (14) | 2.0254 (13) |
Ni—P | 2.154 (2) | 2.1524 (6) | 2.1493 (5) | 2.1507 (11) | 2.1340 (15) | 2.1346 (13) |
P—C1 | 1.837 (5) | 1.832 (2) | 1.8340 (14) | 1.834 (4) | 1.833 (4) | 1.836 (4) |
P—C2 | 1.814 (4) | 1.820 (2) | 1.8200 (14) | 1.808 (3) | 1.800 (4) | 1.800 (4) |
P—C8 | 1.818 (4) | 1.816 (2) | 1.8150 (14) | 1.811 (3) | 1.792 (6) | 1.804 (4) |
C1—C1i | 1.516 (11) | 1.508 (3) | 1.515 (3) | 1.523 (7) | 1.400 (11) | 1.413 (10) |
Ni—P—C1 | 108.3 (2) | 108.33 (6) | 108.54 (6) | 109.27 (12) | 108.68 (15) | 108.77 (16) |
Ni—P—C2 | 113.34 (13) | 113.50 (6) | 113.19 (6) | 110.98 (12) | 112.12 (19) | 111.42 (17) |
Ni—P—C8 | 116.66 (13) | 116.81 (6) | 116.61 (6) | 119.43 (12) | 116.12 (16) | 116.05 (15) |
Cl—Ni—Cli | 94.60 (9) | 94.59 (3) | 94.69 (3) | 95.47 (4) | 96.51 (8) | 97.45 (7) |
Cl—Ni—P | 89.29 (6) | 89.32 (2) | 89.36 (2) | 88.84 (4) | 88.13 (4) | 87.78 (4) |
Cl—Ni—Pi | 173.18 (8) | 173.13 (3) | 172.98 (2) | 175.12 (5) | 174.60 (7) | 173.87 (6) |
P—Ni—Pi | 87.24 (10) | 87.18 (3) | 86.99 (2) | 86.93 (4) | 87.38 (8) | 87.18 (7) |
C1—P—C2 | 103.8 (2) | 104.00 (9) | 104.03 (8) | 104.85 (14) | 105.5 (3) | 105.9 (2) |
C1—P—C8 | 104.5 (2) | 104.71 (8) | 104.30 (8) | 104.80 (14) | 105.7 (3) | 106.0 (2) |
C2—P—C8 | 109.0 (2) | 108.30 (8) | 108.98 (8) | 106.35 (14) | 108.0 (2) | 108.1 (2) |
P—C1—C1i | 106.8 (3) | 107.08 (14) | 106.56 (11) | 107.0 (2) | 110.7 (3) | 109.9 (3) |
P-C1-C1i-Pi | 49.6 (6) | 49.3 (2) | 49.90 (18) | 47.8 (4) | 40.6 (8) | -42.7 (6) |
The bond and angle designations are those appropriate for the symmetric molecules of C (symmetry operation i: -x,y,-z) and therefore data for A (PIFDUD: Busby et al., 1993), A' (PIFDUD01: Davies et al., 1998), A(150) (this work) and B (FUJXUD: Spek et al., 1987) are for the most part given as pairwise mean values with su's adjusted accordingly. For all except A(150), C(293) and C(150) PLATON (Spek, 1990) was used to compute distances and angles from cif data from the Cambridge structural database. |
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The Cambridge Structural Database (Allen & Kennard, 1993) accessed at the chemical database service of the EPSRC (Fletcher et al., 1996) provides three reports of structures for the title compound. Spek et al. (1987) reported the structure of the dichloromethane solvate (FUJXUD) which was subsequently re-examined by Busby et al. (1993) and designated form B along with a second unsolvated structure (form A - PIFDUD). The structure of form A was later determined with greater precision (PIFDUD01: Davies et al., 1998). Following the notation of Busby et al. (1993) we designate the polymorph described here as form C. In the following discussion the various structures (polymorphs) are designated simply by letter as A, B or C and in addition the 150 and 293 K structures presented here are further differentiated as A(150), C(150) and C(293). \sch
The molecules of C (Fig. 1) contain a twofold crystallographic symmetry axis passing through Ni and the mid-point of the C1—C1i bond, symmetry operation i: -x,y,-z. Thus, in addition to Ni in the 2a special positions of the space group I2 the asymmetric unit consists of one Cl and half of the ligand comprising P, the ethane C1 and C2 to C13 of the phenyl groups attached to P. The latter are in the 4 b general positions. According to Busby et al. (1993) molecules of B possess similar but non-crystallographic twofold axial symmetry while those of A do not due to the disposition of the phenyl groups. In all of the polymorphs the coordination of Ni remains essentially similar in the form of a slight tetrahedral distortion from a square-planar arrangement.
Solely on the basis of the mode of preparation of C (see below) it was assumed initially that in forming the complex C the original trans substituted diphosphinoalkene had simply undergone transformation to the cis form. However the length of the putative C═C bond provoked investigation of a model with two rather than one H attached to C1 resulting in a small but significant improvement in the R factor. The correctness of this model was confirmed by proton NMR and supported by elemental analysis and the discovery of crystals of A in admixture with C, one of which was used to provide intensity data at 150 K [A(150)] whose analysis is presented here merely for comparison purposes (Fig. 2 and Table 3).
It follows that in the synthesis of C, accompanied by some A, by the method described below the initial phosphine disubstituted alkene ligand has undergone hydrogenation. This is comparable with the dihalobis(triphenylphosphine)nickel(II) catalysed hydrogenation of methyl linoleate with THF as the hydrogen source (Itatani & Bailar, 1967) supported by the detailed investigation of the generation of H2 in a similar system as reported by Davies et al. (1998).
In the scheme, molecules of A, B and C are handed because relative to the immediate coordination of Ni with Cl down below the plane of the paper (small rectangles) the C—C ethane bond of the ligand may be either rotated clockwise (i) or anticlockwise (ii). Centrosymmetric A and B are racemic in this respect but C is not. By coincidence the molecules of C(293) correspond to i and those of C(150), with a second crystal, to ii.
Table 3 shows that the molecules of A, B and C are very similar except that the ethane C—C of the ligand is approximately 0.1 Å shorter in C than in A or B. The dihedral angles around this bond, while of opposite sign for the enantiomers C(293) and C(150), are smaller in magnitude than the corresponding values in A or B.
Short C—C bonds in ligands of this type are by no means uncommon and extreme cases are, for example, values of 1.380 (10) Å in trans-bis[1,2-bis(dimethylphosphino)ethane]-P,P'-dichlorochromium(II) (DAJDUN: Girolami et al., 1985) or 1.326 (10) Å in dichlorobis[1,2-bis(dimethylphosphino)ethane]iron(II) (BAWSOH: di Vaira et al., 1981) and are usually accounted for by disorder or extreme thermal displacement or a combination of both. However, in the case of C the complete success of the refinement of the absolute structure in both instances with no evidence of twinning or any other form of disorder leaves the shortness of the ethane C—C bond still to be accounted for by other means. Decrease in the temperature of data collection from 293 to 150 K has no effect on this C—C bond length in A but causes an increase in length by about 1% in C. This can be attributed to libration in the case of C but the change is small compared with the overall discrepancy between C and A or B. There is, however, one feature in the structure of C which is totally absent in A or B. This is the hydrogen-bond type contact of the form C1—H1A···Cl present in Fig. 3 and Tables 1 and 2 which interconnects the molecules in columns propagated in the direction of the polar axis b. In this arrangement Cl donates electron density to the alkyl H which is then presumed to release electron density to the C to which it is attached thus imparting some double bond character to the C—C bond and thus shortening it. If this is the case the effect is surprisingly large. There is also present in C an aryl H contact of the form C12—H12.·Cl which serves to interconnect the columns of molecules in sheets parallel to (1,0,1). Both of these contacts were elucidated by means of PLATON (Spek, 1990).