Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270104008479/fr1470sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270104008479/fr1470IVsup2.hkl |
CCDC reference: 243574
A 50 ml Schlenk tube was charged with (III) (0.198 g., 0.5 mmol), [PdCl2(PPh3)]2 (0.219 g., 0.25 mmol) and toluene (5 ml). The mixture was heated under reflux for 4 h, after which the solution was cooled to room temperature and hexane (10 ml) was added. The resutling orange precipitate was filtered off and recrystallized from CH2Cl2/Et2O (yield 0.122 g, 65%; m.p. 546 K). Calculated for PdPCl2C37H38N2: C 61.81, H 5.33, N 3.90%; found: C 61.37, H 4.53, N 4.67%. 1H NMR (400 MHz, CDCl3): δ 7.88 (d, J=1.9 Hz, 2H, Ar), 7.31–7.15 (m, 19H, Ar, PPh3), 4.09 (s, 4H, NCH2CH2N), 2.46, 2.44 (12H, N—CH3). 13C{H} NMR (400 MHz, CDCl3): δ 196.87 (d, 2JC-P=180.8 Hz, C—Pd), 137.58, 136.44, 135.30 (C6, C7, C9), 134.41(d, JC-P=11.30 Hz, o-PC6H5), 131.34, 129.99, 129.47, 126.63 (C8, C10, C11, p-PC6H5), 129.80(d, JC-P=42.4 Hz, ipso-C, PC6H5), 127.24 (d, JC-P=10.0 Hz, m-C PC6H5), 51.95 (NCH2CH2N), 20.84, 18.04 (o-CH3, p-CH3); 31P{H} NMR (400 MHz, CDCl3): δ 19.46.
H atoms were treated as riding atoms, with C—H distances of 0.93 Å for aromatic H atoms, 0.96 Å for methyl H atoms and 0.97 Å for methylene H atoms.
Data collection: X-AREA (Stoe & Cie, 2002); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXL97.
Fig. 1. A view of the title compound, showing the labelling of the non-H atoms. Displacement ellipsoids are shown at the 30% probability level and H atoms have been omitted for clarity. |
[PdCl2(C19H22N2)(C18H15P)] | F(000) = 1472 |
Mr = 717.96 | Dx = 1.395 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 26499 reflections |
a = 13.9423 (6) Å | θ = 1.9–29.2° |
b = 14.7120 (8) Å | µ = 0.77 mm−1 |
c = 17.2894 (7) Å | T = 293 K |
β = 105.446 (3)° | Plate, yellow |
V = 3418.3 (3) Å3 | 0.40 × 0.21 × 0.09 mm |
Z = 4 |
STOE IPDS-II diffractometer | 9467 independent reflections |
Radiation source: fine-focus sealed tube | 5018 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.125 |
Detector resolution: 6.67 pixels mm-1 | θmax = 29.8°, θmin = 1.9° |
ϕ or ω? scans | h = −19→17 |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −20→20 |
Tmin = 0.823, Tmax = 0.933 | l = −22→23 |
34434 measured reflections |
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)] = 0.046 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.83 | w = 1/[σ2(Fo2) + (0.0266P)2] where P = (Fo2 + 2Fc2)/3 |
9467 reflections | (Δ/σ)max = 0.001 |
392 parameters | Δρmax = 0.78 e Å−3 |
0 restraints | Δρmin = −1.03 e Å−3 |
[PdCl2(C19H22N2)(C18H15P)] | V = 3418.3 (3) Å3 |
Mr = 717.96 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 13.9423 (6) Å | µ = 0.77 mm−1 |
b = 14.7120 (8) Å | T = 293 K |
c = 17.2894 (7) Å | 0.40 × 0.21 × 0.09 mm |
β = 105.446 (3)° |
STOE IPDS-II diffractometer | 9467 independent reflections |
Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 5018 reflections with I > 2σ(I) |
Tmin = 0.823, Tmax = 0.933 | Rint = 0.125 |
34434 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.094 | H-atom parameters constrained |
S = 0.83 | Δρmax = 0.78 e Å−3 |
9467 reflections | Δρmin = −1.03 e Å−3 |
392 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. |
x | y | z | Uiso*/Ueq | ||
Pd1 | 0.581501 (19) | 0.191257 (17) | 0.819011 (17) | 0.03280 (7) | |
Cl1 | 0.74093 (6) | 0.24804 (6) | 0.83377 (6) | 0.0462 (2) | |
Cl2 | 0.42490 (7) | 0.13202 (7) | 0.79562 (7) | 0.0584 (3) | |
P1 | 0.54544 (6) | 0.31550 (6) | 0.89018 (6) | 0.0365 (2) | |
N1 | 0.5957 (2) | 0.06525 (18) | 0.68530 (19) | 0.0409 (7) | |
N2 | 0.6425 (2) | 0.00169 (18) | 0.80225 (19) | 0.0411 (7) | |
C1 | 0.6110 (2) | 0.0790 (2) | 0.7635 (2) | 0.0369 (8) | |
C2 | 0.6516 (4) | −0.0729 (2) | 0.7478 (3) | 0.0552 (11) | |
H2A | 0.6069 | −0.1225 | 0.7508 | 0.066* | |
H2B | 0.7193 | −0.0957 | 0.7602 | 0.066* | |
C3 | 0.6225 (3) | −0.0279 (2) | 0.6665 (3) | 0.0536 (11) | |
H3A | 0.6776 | −0.0273 | 0.6421 | 0.064* | |
H3B | 0.5662 | −0.0585 | 0.6308 | 0.064* | |
C11 | 0.5698 (3) | 0.1344 (2) | 0.6254 (2) | 0.0375 (8) | |
C12 | 0.6352 (3) | 0.2054 (2) | 0.6272 (2) | 0.0434 (9) | |
H12 | 0.6935 | 0.2090 | 0.6686 | 0.052* | |
C13 | 0.6147 (3) | 0.2713 (3) | 0.5680 (3) | 0.0479 (9) | |
H13 | 0.6594 | 0.3187 | 0.5699 | 0.057* | |
C14 | 0.5286 (3) | 0.2672 (3) | 0.5062 (2) | 0.0474 (9) | |
C15 | 0.4633 (3) | 0.1974 (3) | 0.5068 (2) | 0.0492 (9) | |
H15 | 0.4045 | 0.1951 | 0.4659 | 0.059* | |
C16 | 0.4801 (3) | 0.1302 (2) | 0.5650 (2) | 0.0441 (9) | |
C17 | 0.5084 (3) | 0.3360 (3) | 0.4386 (3) | 0.0680 (13) | |
H17A | 0.4386 | 0.3367 | 0.4119 | 0.102* | |
H17B | 0.5452 | 0.3198 | 0.4010 | 0.102* | |
H17C | 0.5287 | 0.3953 | 0.4601 | 0.102* | |
C18 | 0.4033 (3) | 0.0586 (3) | 0.5646 (3) | 0.0677 (13) | |
H18A | 0.3972 | 0.0500 | 0.6181 | 0.102* | |
H18B | 0.4231 | 0.0025 | 0.5450 | 0.102* | |
H18C | 0.3403 | 0.0775 | 0.5303 | 0.102* | |
C21 | 0.6752 (3) | −0.0055 (2) | 0.8881 (2) | 0.0417 (8) | |
C22 | 0.6166 (3) | −0.0476 (2) | 0.9315 (2) | 0.0463 (9) | |
C23 | 0.6534 (3) | −0.0498 (3) | 1.0135 (3) | 0.0563 (11) | |
H23 | 0.6147 | −0.0768 | 1.0434 | 0.068* | |
C24 | 0.7446 (3) | −0.0141 (3) | 1.0541 (3) | 0.0545 (10) | |
C25 | 0.8010 (3) | 0.0275 (3) | 1.0090 (3) | 0.0545 (10) | |
H25 | 0.8624 | 0.0528 | 1.0345 | 0.065* | |
C26 | 0.7665 (3) | 0.0314 (2) | 0.9272 (3) | 0.0480 (9) | |
H26 | 0.8050 | 0.0592 | 0.8975 | 0.058* | |
C27 | 0.7818 (4) | −0.0189 (4) | 1.1441 (3) | 0.0824 (16) | |
H27A | 0.8510 | −0.0028 | 1.1603 | 0.124* | |
H27B | 0.7734 | −0.0795 | 1.1617 | 0.124* | |
H27C | 0.7447 | 0.0228 | 1.1677 | 0.124* | |
C28 | 0.5170 (3) | −0.0894 (3) | 0.8903 (3) | 0.0700 (13) | |
H28A | 0.4798 | −0.0481 | 0.8505 | 0.105* | |
H28B | 0.4807 | −0.1013 | 0.9293 | 0.105* | |
H28C | 0.5272 | −0.1453 | 0.8650 | 0.105* | |
C31 | 0.5813 (3) | 0.4219 (2) | 0.8528 (2) | 0.0407 (8) | |
C32 | 0.6212 (3) | 0.4951 (2) | 0.9006 (3) | 0.0528 (10) | |
H32 | 0.6343 | 0.4905 | 0.9561 | 0.063* | |
C33 | 0.6417 (4) | 0.5751 (3) | 0.8664 (4) | 0.0708 (14) | |
H33 | 0.6690 | 0.6238 | 0.8991 | 0.085* | |
C34 | 0.6224 (4) | 0.5835 (3) | 0.7858 (4) | 0.0743 (15) | |
H34 | 0.6351 | 0.6383 | 0.7636 | 0.089* | |
C35 | 0.5841 (3) | 0.5115 (3) | 0.7365 (3) | 0.0656 (13) | |
H35 | 0.5719 | 0.5167 | 0.6811 | 0.079* | |
C36 | 0.5639 (3) | 0.4303 (3) | 0.7710 (3) | 0.0557 (11) | |
H36 | 0.5384 | 0.3812 | 0.7381 | 0.067* | |
C41 | 0.6068 (3) | 0.3086 (2) | 0.9971 (2) | 0.0429 (8) | |
C42 | 0.6866 (3) | 0.2523 (3) | 1.0238 (3) | 0.0595 (11) | |
H42 | 0.7096 | 0.2184 | 0.9870 | 0.071* | |
C43 | 0.7342 (4) | 0.2448 (4) | 1.1056 (3) | 0.0783 (15) | |
H43 | 0.7900 | 0.2080 | 1.1228 | 0.094* | |
C44 | 0.6987 (4) | 0.2914 (3) | 1.1597 (3) | 0.0712 (13) | |
H44 | 0.7290 | 0.2849 | 1.2143 | 0.085* | |
C45 | 0.6186 (4) | 0.3477 (3) | 1.1344 (3) | 0.0779 (15) | |
H45 | 0.5945 | 0.3795 | 1.1717 | 0.093* | |
C46 | 0.5734 (4) | 0.3573 (3) | 1.0531 (3) | 0.0668 (13) | |
H46 | 0.5200 | 0.3970 | 1.0361 | 0.080* | |
C51 | 0.4150 (3) | 0.3344 (2) | 0.8878 (2) | 0.0415 (9) | |
C52 | 0.3577 (3) | 0.4013 (3) | 0.8428 (3) | 0.0662 (13) | |
H52 | 0.3857 | 0.4414 | 0.8134 | 0.079* | |
C53 | 0.2569 (4) | 0.4093 (4) | 0.8410 (4) | 0.0862 (17) | |
H53 | 0.2183 | 0.4547 | 0.8103 | 0.103* | |
C54 | 0.2155 (4) | 0.3513 (3) | 0.8834 (4) | 0.0767 (15) | |
H54 | 0.1487 | 0.3573 | 0.8822 | 0.092* | |
C55 | 0.2714 (3) | 0.2842 (3) | 0.9280 (3) | 0.0732 (14) | |
H55 | 0.2427 | 0.2441 | 0.9569 | 0.088* | |
C56 | 0.3707 (3) | 0.2757 (3) | 0.9301 (3) | 0.0641 (13) | |
H56 | 0.4084 | 0.2297 | 0.9607 | 0.077* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.03365 (12) | 0.03134 (11) | 0.03364 (15) | 0.00241 (12) | 0.00936 (9) | 0.00011 (13) |
Cl1 | 0.0380 (5) | 0.0491 (5) | 0.0518 (6) | −0.0045 (4) | 0.0127 (4) | −0.0033 (4) |
Cl2 | 0.0397 (5) | 0.0633 (6) | 0.0740 (8) | −0.0095 (4) | 0.0179 (5) | −0.0132 (5) |
P1 | 0.0407 (4) | 0.0325 (4) | 0.0379 (6) | 0.0045 (4) | 0.0133 (4) | 0.0012 (4) |
N1 | 0.0531 (18) | 0.0359 (14) | 0.034 (2) | 0.0032 (13) | 0.0115 (14) | −0.0039 (13) |
N2 | 0.0507 (18) | 0.0349 (15) | 0.039 (2) | 0.0041 (13) | 0.0137 (14) | 0.0002 (13) |
C1 | 0.0341 (18) | 0.0344 (17) | 0.040 (2) | 0.0003 (14) | 0.0052 (15) | 0.0016 (15) |
C2 | 0.086 (3) | 0.0371 (19) | 0.045 (3) | 0.011 (2) | 0.023 (2) | −0.0009 (18) |
C3 | 0.068 (3) | 0.0355 (19) | 0.059 (3) | 0.0051 (18) | 0.019 (2) | −0.0097 (18) |
C11 | 0.0450 (19) | 0.0398 (18) | 0.029 (2) | 0.0063 (15) | 0.0123 (15) | −0.0010 (14) |
C12 | 0.0427 (19) | 0.045 (2) | 0.039 (2) | −0.0009 (16) | 0.0059 (15) | 0.0015 (16) |
C13 | 0.045 (2) | 0.0468 (19) | 0.053 (3) | −0.0027 (16) | 0.0137 (18) | 0.0025 (18) |
C14 | 0.047 (2) | 0.050 (2) | 0.046 (3) | 0.0060 (17) | 0.0147 (18) | 0.0094 (18) |
C15 | 0.0401 (18) | 0.059 (2) | 0.044 (2) | 0.0033 (19) | 0.0047 (16) | 0.001 (2) |
C16 | 0.048 (2) | 0.0445 (19) | 0.039 (3) | −0.0034 (16) | 0.0109 (17) | −0.0035 (17) |
C17 | 0.056 (3) | 0.076 (3) | 0.069 (4) | 0.009 (2) | 0.011 (2) | 0.029 (2) |
C18 | 0.060 (3) | 0.071 (3) | 0.066 (3) | −0.017 (2) | 0.006 (2) | 0.006 (2) |
C21 | 0.048 (2) | 0.0343 (17) | 0.043 (3) | 0.0059 (15) | 0.0117 (17) | 0.0047 (16) |
C22 | 0.052 (2) | 0.0428 (19) | 0.044 (3) | 0.0029 (17) | 0.0127 (18) | 0.0105 (17) |
C23 | 0.066 (3) | 0.056 (2) | 0.050 (3) | −0.004 (2) | 0.022 (2) | 0.015 (2) |
C24 | 0.064 (3) | 0.059 (2) | 0.038 (3) | 0.006 (2) | 0.009 (2) | 0.0073 (19) |
C25 | 0.048 (2) | 0.063 (2) | 0.052 (3) | 0.0009 (19) | 0.012 (2) | 0.009 (2) |
C26 | 0.047 (2) | 0.053 (2) | 0.047 (3) | 0.0045 (17) | 0.0180 (18) | 0.0076 (18) |
C27 | 0.084 (4) | 0.112 (4) | 0.049 (4) | −0.012 (3) | 0.013 (3) | 0.011 (3) |
C28 | 0.071 (3) | 0.071 (3) | 0.068 (4) | −0.021 (2) | 0.019 (2) | 0.003 (2) |
C31 | 0.0395 (19) | 0.0394 (18) | 0.046 (3) | 0.0060 (15) | 0.0161 (17) | 0.0033 (17) |
C32 | 0.055 (2) | 0.046 (2) | 0.061 (3) | −0.0004 (18) | 0.022 (2) | −0.0016 (19) |
C33 | 0.072 (3) | 0.042 (2) | 0.104 (5) | −0.014 (2) | 0.033 (3) | −0.001 (3) |
C34 | 0.068 (3) | 0.055 (3) | 0.105 (5) | −0.007 (2) | 0.033 (3) | 0.026 (3) |
C35 | 0.059 (3) | 0.080 (3) | 0.059 (3) | 0.003 (2) | 0.017 (2) | 0.030 (3) |
C36 | 0.060 (3) | 0.052 (2) | 0.056 (3) | −0.0012 (19) | 0.017 (2) | 0.008 (2) |
C41 | 0.053 (2) | 0.0375 (16) | 0.038 (2) | 0.0014 (18) | 0.0114 (16) | 0.0008 (17) |
C42 | 0.061 (3) | 0.073 (3) | 0.043 (3) | 0.015 (2) | 0.010 (2) | −0.001 (2) |
C43 | 0.072 (3) | 0.105 (4) | 0.050 (4) | 0.025 (3) | 0.002 (2) | 0.005 (3) |
C44 | 0.082 (3) | 0.084 (3) | 0.040 (3) | −0.008 (3) | 0.004 (2) | 0.001 (2) |
C45 | 0.102 (4) | 0.084 (3) | 0.047 (4) | 0.005 (3) | 0.019 (3) | −0.016 (3) |
C46 | 0.078 (3) | 0.064 (3) | 0.056 (3) | 0.021 (2) | 0.015 (2) | −0.010 (2) |
C51 | 0.050 (2) | 0.0359 (17) | 0.043 (2) | 0.0045 (14) | 0.0211 (17) | −0.0043 (15) |
C52 | 0.054 (3) | 0.063 (3) | 0.088 (4) | 0.020 (2) | 0.031 (2) | 0.024 (2) |
C53 | 0.057 (3) | 0.098 (4) | 0.109 (5) | 0.034 (3) | 0.032 (3) | 0.036 (3) |
C54 | 0.054 (3) | 0.078 (3) | 0.111 (5) | 0.009 (2) | 0.043 (3) | −0.003 (3) |
C55 | 0.065 (3) | 0.071 (3) | 0.098 (4) | 0.001 (2) | 0.048 (3) | 0.009 (3) |
C56 | 0.057 (3) | 0.057 (2) | 0.087 (4) | 0.008 (2) | 0.033 (2) | 0.021 (2) |
Pd1—C1 | 2.008 (3) | C25—C26 | 1.368 (6) |
Pd1—Cl2 | 2.2847 (10) | C25—H25 | 0.9300 |
Pd1—Cl1 | 2.3242 (9) | C26—H26 | 0.9300 |
Pd1—P1 | 2.3318 (9) | C27—H27A | 0.9600 |
P1—C31 | 1.813 (4) | C27—H27B | 0.9600 |
P1—C41 | 1.822 (4) | C27—H27C | 0.9600 |
P1—C51 | 1.830 (4) | C28—H28A | 0.9600 |
N1—C1 | 1.326 (5) | C28—H28B | 0.9600 |
N1—C11 | 1.428 (4) | C28—H28C | 0.9600 |
N1—C3 | 1.479 (4) | C31—C36 | 1.376 (5) |
N2—C1 | 1.334 (4) | C31—C32 | 1.381 (5) |
N2—C21 | 1.437 (5) | C32—C33 | 1.382 (6) |
N2—C2 | 1.473 (5) | C32—H32 | 0.9300 |
C2—C3 | 1.508 (6) | C33—C34 | 1.353 (7) |
C2—H2A | 0.9700 | C33—H33 | 0.9300 |
C2—H2B | 0.9700 | C34—C35 | 1.376 (7) |
C3—H3A | 0.9700 | C34—H34 | 0.9300 |
C3—H3B | 0.9700 | C35—C36 | 1.396 (6) |
C11—C12 | 1.383 (5) | C35—H35 | 0.9300 |
C11—C16 | 1.400 (5) | C36—H36 | 0.9300 |
C12—C13 | 1.383 (5) | C41—C42 | 1.364 (5) |
C12—H12 | 0.9300 | C41—C46 | 1.382 (6) |
C13—C14 | 1.381 (5) | C42—C43 | 1.397 (6) |
C13—H13 | 0.9300 | C42—H42 | 0.9300 |
C14—C15 | 1.375 (5) | C43—C44 | 1.355 (7) |
C14—C17 | 1.514 (5) | C43—H43 | 0.9300 |
C15—C16 | 1.386 (5) | C44—C45 | 1.366 (7) |
C15—H15 | 0.9300 | C44—H44 | 0.9300 |
C16—C18 | 1.501 (5) | C45—C46 | 1.385 (7) |
C17—H17A | 0.9600 | C45—H45 | 0.9300 |
C17—H17B | 0.9600 | C46—H46 | 0.9300 |
C17—H17C | 0.9600 | C51—C52 | 1.372 (5) |
C18—H18A | 0.9600 | C51—C56 | 1.379 (5) |
C18—H18B | 0.9600 | C52—C53 | 1.402 (6) |
C18—H18C | 0.9600 | C52—H52 | 0.9300 |
C21—C26 | 1.384 (5) | C53—C54 | 1.351 (7) |
C21—C22 | 1.392 (5) | C53—H53 | 0.9300 |
C22—C23 | 1.374 (6) | C54—C55 | 1.363 (7) |
C22—C28 | 1.512 (6) | C54—H54 | 0.9300 |
C23—C24 | 1.383 (6) | C55—C56 | 1.381 (6) |
C23—H23 | 0.9300 | C55—H55 | 0.9300 |
C24—C25 | 1.388 (6) | C56—H56 | 0.9300 |
C24—C27 | 1.505 (6) | ||
C1—Pd1—Cl2 | 84.80 (10) | C25—C24—C27 | 120.7 (4) |
C1—Pd1—Cl1 | 92.09 (10) | C26—C25—C24 | 120.2 (4) |
Cl2—Pd1—Cl1 | 175.94 (4) | C26—C25—H25 | 119.9 |
C1—Pd1—P1 | 176.23 (11) | C24—C25—H25 | 119.9 |
Cl2—Pd1—P1 | 93.57 (4) | C25—C26—C21 | 120.8 (4) |
Cl1—Pd1—P1 | 89.69 (3) | C25—C26—H26 | 119.6 |
C31—P1—C41 | 108.08 (18) | C21—C26—H26 | 119.6 |
C31—P1—C51 | 103.16 (16) | C24—C27—H27A | 109.5 |
C41—P1—C51 | 103.09 (17) | C24—C27—H27B | 109.5 |
C31—P1—Pd1 | 111.71 (13) | H27A—C27—H27B | 109.5 |
C41—P1—Pd1 | 112.50 (12) | C24—C27—H27C | 109.5 |
C51—P1—Pd1 | 117.39 (12) | H27A—C27—H27C | 109.5 |
C1—N1—C11 | 124.9 (3) | H27B—C27—H27C | 109.5 |
C1—N1—C3 | 112.5 (3) | C22—C28—H28A | 109.5 |
C11—N1—C3 | 122.0 (3) | C22—C28—H28B | 109.5 |
C1—N2—C21 | 123.6 (3) | H28A—C28—H28B | 109.5 |
C1—N2—C2 | 112.7 (3) | C22—C28—H28C | 109.5 |
C21—N2—C2 | 123.2 (3) | H28A—C28—H28C | 109.5 |
N1—C1—N2 | 108.9 (3) | H28B—C28—H28C | 109.5 |
N1—C1—Pd1 | 128.0 (2) | C36—C31—C32 | 118.5 (4) |
N2—C1—Pd1 | 122.9 (3) | C36—C31—P1 | 117.0 (3) |
N2—C2—C3 | 102.8 (3) | C32—C31—P1 | 124.4 (3) |
N2—C2—H2A | 111.2 | C31—C32—C33 | 120.3 (5) |
C3—C2—H2A | 111.2 | C31—C32—H32 | 119.9 |
N2—C2—H2B | 111.2 | C33—C32—H32 | 119.9 |
C3—C2—H2B | 111.2 | C34—C33—C32 | 120.8 (5) |
H2A—C2—H2B | 109.1 | C34—C33—H33 | 119.6 |
N1—C3—C2 | 102.9 (3) | C32—C33—H33 | 119.6 |
N1—C3—H3A | 111.2 | C33—C34—C35 | 120.4 (4) |
C2—C3—H3A | 111.2 | C33—C34—H34 | 119.8 |
N1—C3—H3B | 111.2 | C35—C34—H34 | 119.8 |
C2—C3—H3B | 111.2 | C34—C35—C36 | 118.9 (5) |
H3A—C3—H3B | 109.1 | C34—C35—H35 | 120.5 |
C12—C11—C16 | 120.2 (3) | C36—C35—H35 | 120.5 |
C12—C11—N1 | 118.9 (3) | C31—C36—C35 | 121.1 (4) |
C16—C11—N1 | 120.9 (3) | C31—C36—H36 | 119.5 |
C13—C12—C11 | 120.5 (3) | C35—C36—H36 | 119.5 |
C13—C12—H12 | 119.7 | C42—C41—C46 | 118.3 (4) |
C11—C12—H12 | 119.7 | C42—C41—P1 | 119.8 (3) |
C14—C13—C12 | 120.6 (4) | C46—C41—P1 | 121.8 (3) |
C14—C13—H13 | 119.7 | C41—C42—C43 | 121.0 (4) |
C12—C13—H13 | 119.7 | C41—C42—H42 | 119.5 |
C15—C14—C13 | 117.8 (4) | C43—C42—H42 | 119.5 |
C15—C14—C17 | 121.3 (4) | C44—C43—C42 | 119.8 (5) |
C13—C14—C17 | 120.9 (4) | C44—C43—H43 | 120.1 |
C14—C15—C16 | 123.7 (3) | C42—C43—H43 | 120.1 |
C14—C15—H15 | 118.1 | C43—C44—C45 | 120.1 (5) |
C16—C15—H15 | 118.1 | C43—C44—H44 | 119.9 |
C15—C16—C11 | 117.0 (3) | C45—C44—H44 | 119.9 |
C15—C16—C18 | 121.0 (3) | C44—C45—C46 | 120.1 (5) |
C11—C16—C18 | 122.0 (4) | C44—C45—H45 | 120.0 |
C14—C17—H17A | 109.5 | C46—C45—H45 | 120.0 |
C14—C17—H17B | 109.5 | C41—C46—C45 | 120.6 (4) |
H17A—C17—H17B | 109.5 | C41—C46—H46 | 119.7 |
C14—C17—H17C | 109.5 | C45—C46—H46 | 119.7 |
H17A—C17—H17C | 109.5 | C52—C51—C56 | 118.4 (4) |
H17B—C17—H17C | 109.5 | C52—C51—P1 | 123.1 (3) |
C16—C18—H18A | 109.5 | C56—C51—P1 | 118.4 (3) |
C16—C18—H18B | 109.5 | C51—C52—C53 | 120.0 (4) |
H18A—C18—H18B | 109.5 | C51—C52—H52 | 120.0 |
C16—C18—H18C | 109.5 | C53—C52—H52 | 120.0 |
H18A—C18—H18C | 109.5 | C54—C53—C52 | 120.4 (5) |
H18B—C18—H18C | 109.5 | C54—C53—H53 | 119.8 |
C26—C21—C22 | 120.5 (4) | C52—C53—H53 | 119.8 |
C26—C21—N2 | 118.3 (3) | C53—C54—C55 | 120.1 (4) |
C22—C21—N2 | 121.2 (3) | C53—C54—H54 | 120.0 |
C23—C22—C21 | 117.0 (4) | C55—C54—H54 | 120.0 |
C23—C22—C28 | 121.3 (4) | C54—C55—C56 | 120.0 (4) |
C21—C22—C28 | 121.7 (4) | C54—C55—H55 | 120.0 |
C22—C23—C24 | 123.8 (4) | C56—C55—H55 | 120.0 |
C22—C23—H23 | 118.1 | C51—C56—C55 | 121.1 (4) |
C24—C23—H23 | 118.1 | C51—C56—H56 | 119.5 |
C23—C24—C25 | 117.6 (4) | C55—C56—H56 | 119.5 |
C23—C24—C27 | 121.6 (4) | ||
Cl2—Pd1—P1—C31 | −129.05 (14) | C22—C23—C24—C25 | 1.1 (6) |
Cl1—Pd1—P1—C31 | 48.52 (13) | C22—C23—C24—C27 | −179.5 (4) |
Cl2—Pd1—P1—C41 | 109.18 (13) | C23—C24—C25—C26 | −0.7 (6) |
Cl1—Pd1—P1—C41 | −73.25 (13) | C27—C24—C25—C26 | 179.9 (4) |
Cl2—Pd1—P1—C51 | −10.21 (14) | C24—C25—C26—C21 | 0.2 (6) |
Cl1—Pd1—P1—C51 | 167.36 (14) | C22—C21—C26—C25 | −0.2 (6) |
C11—N1—C1—N2 | −174.5 (3) | N2—C21—C26—C25 | 179.3 (3) |
C3—N1—C1—N2 | −2.7 (4) | C41—P1—C31—C36 | 164.0 (3) |
C11—N1—C1—Pd1 | 11.0 (5) | C51—P1—C31—C36 | −87.3 (3) |
C3—N1—C1—Pd1 | −177.3 (3) | Pd1—P1—C31—C36 | 39.7 (3) |
C21—N2—C1—N1 | 173.8 (3) | C41—P1—C31—C32 | −18.3 (4) |
C2—N2—C1—N1 | 0.7 (4) | C51—P1—C31—C32 | 90.4 (3) |
C21—N2—C1—Pd1 | −11.3 (5) | Pd1—P1—C31—C32 | −142.6 (3) |
C2—N2—C1—Pd1 | 175.6 (3) | C36—C31—C32—C33 | 0.9 (6) |
Cl2—Pd1—C1—N1 | 84.9 (3) | P1—C31—C32—C33 | −176.8 (3) |
Cl1—Pd1—C1—N1 | −92.4 (3) | C31—C32—C33—C34 | 0.5 (7) |
Cl2—Pd1—C1—N2 | −88.9 (3) | C32—C33—C34—C35 | −1.5 (7) |
Cl1—Pd1—C1—N2 | 93.7 (3) | C33—C34—C35—C36 | 1.1 (7) |
C1—N2—C2—C3 | 1.4 (4) | C32—C31—C36—C35 | −1.3 (6) |
C21—N2—C2—C3 | −171.7 (3) | P1—C31—C36—C35 | 176.5 (3) |
C1—N1—C3—C2 | 3.5 (4) | C34—C35—C36—C31 | 0.3 (7) |
C11—N1—C3—C2 | 175.5 (3) | C31—P1—C41—C42 | −105.0 (3) |
N2—C2—C3—N1 | −2.7 (4) | C51—P1—C41—C42 | 146.3 (3) |
C1—N1—C11—C12 | 61.6 (5) | Pd1—P1—C41—C42 | 18.8 (4) |
C3—N1—C11—C12 | −109.4 (4) | C31—P1—C41—C46 | 76.7 (4) |
C1—N1—C11—C16 | −119.0 (4) | C51—P1—C41—C46 | −32.0 (4) |
C3—N1—C11—C16 | 70.0 (5) | Pd1—P1—C41—C46 | −159.5 (3) |
C16—C11—C12—C13 | −2.4 (5) | C46—C41—C42—C43 | −0.8 (7) |
N1—C11—C12—C13 | 177.0 (3) | P1—C41—C42—C43 | −179.2 (4) |
C11—C12—C13—C14 | 0.1 (6) | C41—C42—C43—C44 | 2.5 (8) |
C12—C13—C14—C15 | 1.7 (6) | C42—C43—C44—C45 | −2.1 (8) |
C12—C13—C14—C17 | −176.5 (4) | C43—C44—C45—C46 | 0.0 (8) |
C13—C14—C15—C16 | −1.3 (6) | C42—C41—C46—C45 | −1.3 (7) |
C17—C14—C15—C16 | 176.9 (4) | P1—C41—C46—C45 | 177.0 (4) |
C14—C15—C16—C11 | −0.9 (6) | C44—C45—C46—C41 | 1.7 (8) |
C14—C15—C16—C18 | 176.8 (4) | C31—P1—C51—C52 | 18.8 (4) |
C12—C11—C16—C15 | 2.7 (5) | C41—P1—C51—C52 | 131.2 (4) |
N1—C11—C16—C15 | −176.6 (3) | Pd1—P1—C51—C52 | −104.5 (4) |
C12—C11—C16—C18 | −174.9 (4) | C31—P1—C51—C56 | −164.6 (3) |
N1—C11—C16—C18 | 5.8 (6) | C41—P1—C51—C56 | −52.1 (4) |
C1—N2—C21—C26 | −73.0 (4) | Pd1—P1—C51—C56 | 72.1 (4) |
C2—N2—C21—C26 | 99.3 (4) | C56—C51—C52—C53 | 0.4 (7) |
C1—N2—C21—C22 | 106.4 (4) | P1—C51—C52—C53 | 177.1 (4) |
C2—N2—C21—C22 | −81.2 (5) | C51—C52—C53—C54 | 0.0 (9) |
C26—C21—C22—C23 | 0.6 (5) | C52—C53—C54—C55 | −0.5 (9) |
N2—C21—C22—C23 | −178.9 (3) | C53—C54—C55—C56 | 0.4 (9) |
C26—C21—C22—C28 | −179.3 (4) | C52—C51—C56—C55 | −0.5 (7) |
N2—C21—C22—C28 | 1.2 (5) | P1—C51—C56—C55 | −177.3 (4) |
C21—C22—C23—C24 | −1.0 (6) | C54—C55—C56—C51 | 0.1 (8) |
C28—C22—C23—C24 | 178.8 (4) |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C19H22N2)(C18H15P)] |
Mr | 717.96 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 13.9423 (6), 14.7120 (8), 17.2894 (7) |
β (°) | 105.446 (3) |
V (Å3) | 3418.3 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.77 |
Crystal size (mm) | 0.40 × 0.21 × 0.09 |
Data collection | |
Diffractometer | STOE IPDS-II diffractometer |
Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
Tmin, Tmax | 0.823, 0.933 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 34434, 9467, 5018 |
Rint | 0.125 |
(sin θ/λ)max (Å−1) | 0.699 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.094, 0.83 |
No. of reflections | 9467 |
No. of parameters | 392 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.78, −1.03 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-AREA, X-RED32 (Stoe & Cie, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEPIII (Burnett & Johnson, 1996), SHELXL97.
P1—C31 | 1.813 (4) | N1—C11 | 1.428 (4) |
P1—C41 | 1.822 (4) | N2—C21 | 1.437 (5) |
P1—C51 | 1.830 (4) | ||
C1—Pd1—Cl2 | 84.80 (10) | C41—P1—Pd1 | 112.50 (12) |
C1—Pd1—Cl1 | 92.09 (10) | C51—P1—Pd1 | 117.39 (12) |
C31—P1—C41 | 108.08 (18) | N1—C1—N2 | 108.9 (3) |
C31—P1—C51 | 103.16 (16) | N1—C1—Pd1 | 128.0 (2) |
C41—P1—C51 | 103.09 (17) | N2—C1—Pd1 | 122.9 (3) |
C31—P1—Pd1 | 111.71 (13) |
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Recently, increasing attention has been focused on using imidazole-based N-heterocyclic carbene (NHC) compounds as ancillary ligands for a number of transition-metal-mediated catalytic reactions (Bourissou et al., 2000; Perry & Burgess, 2003; Herrmann, 2002). The donating properties of these ligands are superior to those of the most basic phosphanes. The ability of NHCs to coordinate metal centers makes them excellent candidates for the design of well defined catalysts. Increasing knowledge of the chemical properties of ligands and derived complexes has led to growing demand for systems with more and more complex structures. In view of the growing importance of palladium complexes as C—C and C–heteroatom catalysts (Culkin & Hartwig, 2003), we have synthesized and structurally characterized the title compound, (IV).
Trans-coordination of the carbene and one phosphine group to the palladium(II) center is found in the crystal structure, as shown in Fig. 1. The coordination of the ligands is not exactly planar, the deviations of the ligating atoms Cl1, Cl2, P1 and C1 from the plane through these atoms and the Pd atom are −0.054 (1), −0.057 (1), 0.052 (1) and 0.064 (1) Å, respectively. The Pd1/Cl1/Cl2/P1/C1 coordination plane that is formed by the slightly distorted square-planar coordination of the palladium(II) metal center is approximately perpendicular to the plane of the carbene ring [89.35 (12)°], as reported for similar N-heterocyclic carbene complexes (Herrmann et al., 1997; Herrmann et al., 2001). Bond angles at the Pd atom, involving trans pairs of substituents, deviate from the expected 180°, being 176.23 (11)° for the C1—Pd1—P1 angle and 175.94 (4)° for the Cl1—Pd—Cl2 angle. The bonding within the NHC ring indicates a pattern of delocalization that extends from atom N1 to atom N2 through atom C1, the N1—C1 [1.326 (5) Å] and N2—C1 [1.334 (4) Å] distances being significantly shorter than the N2—C2 [1.473 (5) Å] and N1—C3 [1.479 (4) Å] distances, in accordance with a previous study (McGuinness et al., 1998). The Cl2—Pd1—P1 and Cl1—Pd1—P1 bond angles are 93.57 (4) and 89.69 (3)°, respectively. The compression of the bond angles may be attributed to a steric interaction between the Cl atoms and the aromatic rings. There is a significant difference between the two Pd—Cl bond lengths in the title complex [Pd1—Cl2 2.2847 (10) Å and Pd1—Cl1 = 2.3242 (9) Å], probably because of the presence of intramolecular C—H···Cl interactions. There are two intramolecular C—H···Cl interactions with dimensions C12···Cl1 3.538 (3), H12···Cl1 2.81 Å, C12—H12···Cl1 136° and C42···Cl1 3.563 (5), H42···Cl1 = 2.83 Å, C42—H42···Cl1 136°,
The C1—Pd1 bond distance between the NHC ligand and the metal atom is 2.008 (3) Å, comparable to that in other palladium(II)–NHC complexes (Liu et al., 2003; Magill et al., 2001). The Pd—P bond distance [2.3318 (9) Å] is also similar to those reported previously (Aupers et al., 2000; McCrindle et al., 2000). The dihedral angle between the two dimethylphenyl ring planes is 33.17 (13)°.