Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801008728/ya6030sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801008728/ya6030Isup2.hkl |
CCDC reference: 170742
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.013 Å
- Disorder in solvent or counterion
- R factor = 0.063
- wR factor = 0.099
- Data-to-parameter ratio = 16.5
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_302 Alert C Anion/Solvent Disorder ....................... 11.00 Perc. General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _reflns_number_total 12994 Count of symmetry unique reflns 7314 Completeness (_total/calc) 177.66% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 5680 Fraction of Friedel pairs measured 0.777 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
[Pd2(dba)3]·CHCl3 (0.10 g, 0.11 mmol), where dba is dibenzylideneacetone, and dppe (0.08 g, 0.20 mmol) were dissolved in toluene (50 mol) under nitrogen and stirred for 2 h. ClCO2Me (0.02 g, 0.23 mmol) was added and the solution (which turned yellow) was stirred briefly. The solvent was removed in vacuo, the residue was identified as (I) and re-crystallized from deuterochloroform by slow evaporation at room temperature.
All H atoms were treated as 'riding', with C(sp2)—H and C(sp3)—H bond distances of 0.95 and 0.99 Å, U(iso) equal to 1.3 U(eq) of the carrying carbon atom for the methylene H atoms and 1.2 U(eq) for the deuterium atoms and phenyl H atoms. Molecule B1 shows rotational disorder around the threefold molecular axis. The disorder was approximated by two sets of chlorine positions: Cl3B, Cl4B, Cl5B with occupancies 0.85 and Cl3D, Cl4D, Cl5D with occupancies 0.15, but the high residual electron density (up to 1.36 e Å-3) may indicate a continuous rotational disorder. All C—Cl bonds in both orienations of molecule B1 were restrained to similar lengths. Anomalous distribution of reflection intensities, due to the sublattice and the disorder of relatively heavy (Cl) atoms, results in high S and/or weighting scheme parameters. The actual weighting scheme was optimized for the data set, excluding non-positive F2.
Data collection: SMART (Siemens, 1995a); cell refinement: SMART (Siemens, 1995a); data reduction: SAINT (Siemens, 1995a); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); molecular graphics: SHELXTL (Siemens, 1995b); software used to prepare material for publication: SHELXTL (Siemens, 1995b).
C26H24Cl2P2Pd·3(CCl3D) | Dx = 1.634 Mg m−3 |
Mr = 936.81 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 447 reflections |
a = 16.292 (1) Å | θ = 12–23° |
b = 18.404 (1) Å | µ = 1.37 mm−1 |
c = 25.317 (2) Å | T = 150 K |
V = 7591 (1) Å3 | Plate, yellow |
Z = 8 | 0.34 × 0.25 × 0.08 mm |
F(000) = 3712 |
SMART 1K CCD area detector diffractometer | 12994 independent reflections |
Radiation source: fine-focus sealed tube | 9802 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.083 |
Detector resolution: 8 pixels mm-1 | θmax = 25.0°, θmin = 1.4° |
ω scans | h = −18→19 |
Absorption correction: integration XPREP SHELXTL (Siemens, 1995b) | k = −21→21 |
Tmin = 0.701, Tmax = 0.920 | l = −30→27 |
41687 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)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.099 | w = 1/[σ2(Fo2) + 5.0304P] where P = (Fo2 + 2Fc2)/3 |
S = 1.78 | (Δ/σ)max = 0.005 |
12994 reflections | Δρmax = 1.36 e Å−3 |
787 parameters | Δρmin = −0.98 e Å−3 |
15 restraints | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.02 (3) |
C26H24Cl2P2Pd·3(CCl3D) | V = 7591 (1) Å3 |
Mr = 936.81 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 16.292 (1) Å | µ = 1.37 mm−1 |
b = 18.404 (1) Å | T = 150 K |
c = 25.317 (2) Å | 0.34 × 0.25 × 0.08 mm |
SMART 1K CCD area detector diffractometer | 12994 independent reflections |
Absorption correction: integration XPREP SHELXTL (Siemens, 1995b) | 9802 reflections with I > 2σ(I) |
Tmin = 0.701, Tmax = 0.920 | Rint = 0.083 |
41687 measured reflections |
R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
wR(F2) = 0.099 | Δρmax = 1.36 e Å−3 |
S = 1.78 | Δρmin = −0.98 e Å−3 |
12994 reflections | Absolute structure: Flack (1983) |
787 parameters | Absolute structure parameter: −0.02 (3) |
15 restraints |
Experimental. The data collection nominally covered over a hemisphere of reciprocal space, by a combination of 5 sets of ω scans; each set at different ϕ and/or 2θ angles and each scan (25 sec exposure) covering 0.3° in ω. Crystal to detector distance 6.0 cm. 7201 unique reflections (for Laue class) and 5793 Friedel equivalents were measured, of which 5564 and 4238 respectively were observed, I>2σ(I). |
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. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
PdA | 0.65695 (3) | 0.32151 (3) | 0.46803 (3) | 0.02142 (15) | |
Cl1A | 0.79465 (12) | 0.29190 (11) | 0.48789 (9) | 0.0335 (6) | |
Cl2A | 0.69709 (13) | 0.39035 (11) | 0.39369 (9) | 0.0328 (6) | |
P1A | 0.52264 (13) | 0.34504 (10) | 0.45532 (9) | 0.0228 (6) | |
P2A | 0.61517 (12) | 0.25113 (10) | 0.53484 (9) | 0.0235 (5) | |
C1A | 0.4687 (4) | 0.3159 (4) | 0.5156 (3) | 0.0227 (19) | |
H1A1 | 0.4776 | 0.3516 | 0.5443 | 0.030* | |
H1A2 | 0.4090 | 0.3120 | 0.5088 | 0.030* | |
C2A | 0.5043 (4) | 0.2425 (4) | 0.5312 (4) | 0.0262 (19) | |
H2A1 | 0.4894 | 0.2056 | 0.5044 | 0.034* | |
H2A2 | 0.4817 | 0.2271 | 0.5657 | 0.034* | |
C11A | 0.4873 (5) | 0.4364 (4) | 0.4408 (4) | 0.030 (2) | |
C12A | 0.4964 (5) | 0.4644 (4) | 0.3900 (3) | 0.033 (2) | |
H12A | 0.5235 | 0.4370 | 0.3634 | 0.040* | |
C13A | 0.4659 (6) | 0.5326 (5) | 0.3782 (4) | 0.045 (3) | |
H13A | 0.4732 | 0.5526 | 0.3439 | 0.054* | |
C14A | 0.4238 (6) | 0.5728 (5) | 0.4172 (4) | 0.038 (3) | |
H14A | 0.4013 | 0.6189 | 0.4087 | 0.046* | |
C15A | 0.4143 (5) | 0.5452 (4) | 0.4672 (4) | 0.037 (2) | |
H15A | 0.3879 | 0.5731 | 0.4938 | 0.045* | |
C16A | 0.4449 (5) | 0.4766 (4) | 0.4794 (3) | 0.027 (2) | |
H16A | 0.4370 | 0.4570 | 0.5137 | 0.033* | |
C21A | 0.4822 (5) | 0.2902 (4) | 0.4016 (3) | 0.022 (2) | |
C22A | 0.5339 (6) | 0.2488 (5) | 0.3698 (3) | 0.035 (2) | |
H22A | 0.5913 | 0.2477 | 0.3765 | 0.042* | |
C23A | 0.5006 (6) | 0.2079 (5) | 0.3282 (4) | 0.041 (3) | |
H23A | 0.5360 | 0.1802 | 0.3062 | 0.049* | |
C24A | 0.4182 (5) | 0.2073 (4) | 0.3189 (3) | 0.031 (2) | |
H24A | 0.3968 | 0.1795 | 0.2904 | 0.037* | |
C25A | 0.3655 (5) | 0.2482 (4) | 0.3509 (3) | 0.033 (2) | |
H25A | 0.3080 | 0.2475 | 0.3447 | 0.039* | |
C26A | 0.3972 (5) | 0.2892 (4) | 0.3918 (4) | 0.032 (2) | |
H26A | 0.3618 | 0.3176 | 0.4133 | 0.038* | |
C31A | 0.6344 (5) | 0.2899 (4) | 0.5994 (4) | 0.029 (2) | |
C32A | 0.6035 (5) | 0.2587 (5) | 0.6456 (3) | 0.033 (2) | |
H32A | 0.5745 | 0.2140 | 0.6437 | 0.040* | |
C33A | 0.6142 (6) | 0.2921 (5) | 0.6940 (4) | 0.044 (3) | |
H33A | 0.5928 | 0.2701 | 0.7250 | 0.053* | |
C34A | 0.6581 (6) | 0.3557 (6) | 0.6980 (4) | 0.049 (3) | |
H34A | 0.6649 | 0.3783 | 0.7314 | 0.059* | |
C35A | 0.6893 (6) | 0.3871 (5) | 0.6535 (4) | 0.047 (3) | |
H35A | 0.7197 | 0.4309 | 0.6564 | 0.056* | |
C36A | 0.6774 (5) | 0.3562 (4) | 0.6045 (4) | 0.033 (2) | |
H36A | 0.6992 | 0.3791 | 0.5740 | 0.040* | |
C41A | 0.6528 (4) | 0.1581 (3) | 0.5350 (4) | 0.0226 (19) | |
C42A | 0.6333 (5) | 0.1149 (4) | 0.4910 (4) | 0.036 (2) | |
H42A | 0.6018 | 0.1349 | 0.4630 | 0.043* | |
C43A | 0.6606 (6) | 0.0438 (5) | 0.4882 (4) | 0.051 (3) | |
H43A | 0.6448 | 0.0144 | 0.4591 | 0.061* | |
C44A | 0.7098 (5) | 0.0160 (4) | 0.5280 (5) | 0.048 (3) | |
H44A | 0.7298 | −0.0324 | 0.5256 | 0.058* | |
C45A | 0.7289 (5) | 0.0586 (5) | 0.5706 (4) | 0.044 (3) | |
H45A | 0.7623 | 0.0387 | 0.5977 | 0.053* | |
C46A | 0.7020 (5) | 0.1299 (4) | 0.5749 (4) | 0.033 (2) | |
H46A | 0.7173 | 0.1588 | 0.6044 | 0.040* | |
C3A | 0.6846 (5) | 0.4295 (5) | 0.2606 (4) | 0.037 (2) | |
D3A | 0.7139 | 0.4086 | 0.2918 | 0.045* | |
Cl3A | 0.74571 (18) | 0.41476 (15) | 0.20356 (10) | 0.0609 (8) | |
Cl4A | 0.6702 (2) | 0.52241 (14) | 0.27094 (12) | 0.0742 (9) | |
Cl5A | 0.58954 (17) | 0.38406 (16) | 0.25316 (11) | 0.0638 (8) | |
C4A | 0.7942 (5) | 0.2156 (5) | 0.3549 (4) | 0.041 (3) | |
D4A | 0.7873 | 0.2574 | 0.3797 | 0.050* | |
Cl6A | 0.74442 (15) | 0.23637 (14) | 0.29592 (10) | 0.0516 (7) | |
Cl7A | 0.90162 (15) | 0.20215 (15) | 0.34373 (10) | 0.0543 (8) | |
Cl8A | 0.7538 (2) | 0.13782 (16) | 0.38463 (13) | 0.0818 (10) | |
C5A | 0.9008 (6) | 0.4454 (5) | 0.3671 (4) | 0.045 (3) | |
D5A | 0.8626 | 0.4216 | 0.3928 | 0.054* | |
Cl9A | 1.00396 (15) | 0.43416 (14) | 0.39120 (10) | 0.0525 (7) | |
Cl0A | 0.89163 (19) | 0.40210 (18) | 0.30703 (12) | 0.0803 (10) | |
Cl10 | 0.8772 (2) | 0.53581 (17) | 0.36420 (16) | 0.1042 (13) | |
PdB | 0.62381 (3) | 0.82362 (3) | 0.46665 (3) | 0.02195 (15) | |
Cl1B | 0.76307 (12) | 0.80989 (11) | 0.49112 (9) | 0.0363 (6) | |
Cl2B | 0.65480 (14) | 0.89745 (11) | 0.39273 (8) | 0.0318 (5) | |
P1B | 0.48938 (13) | 0.83844 (10) | 0.45201 (8) | 0.0224 (5) | |
P2B | 0.58582 (12) | 0.74672 (10) | 0.53059 (9) | 0.0239 (5) | |
C1B | 0.4341 (5) | 0.8039 (4) | 0.5102 (3) | 0.024 (2) | |
H1B1 | 0.4392 | 0.8386 | 0.5399 | 0.032* | |
H1B2 | 0.3751 | 0.7973 | 0.5021 | 0.032* | |
C2B | 0.4743 (4) | 0.7307 (4) | 0.5252 (3) | 0.025 (2) | |
H2B1 | 0.4627 | 0.6941 | 0.4975 | 0.033* | |
H2B2 | 0.4521 | 0.7127 | 0.5592 | 0.033* | |
C11B | 0.4543 (5) | 0.9310 (4) | 0.4407 (3) | 0.024 (2) | |
C12B | 0.4446 (5) | 0.9577 (4) | 0.3898 (3) | 0.029 (2) | |
H12B | 0.4552 | 0.9269 | 0.3604 | 0.035* | |
C13B | 0.4195 (5) | 1.0285 (5) | 0.3814 (4) | 0.034 (2) | |
H13B | 0.4134 | 1.0467 | 0.3465 | 0.041* | |
C14B | 0.4039 (5) | 1.0733 (5) | 0.4246 (4) | 0.035 (2) | |
H14B | 0.3833 | 1.1210 | 0.4190 | 0.042* | |
C15B | 0.4162 (5) | 1.0482 (4) | 0.4752 (4) | 0.033 (2) | |
H15B | 0.4082 | 1.0797 | 0.5045 | 0.039* | |
C16B | 0.4421 (5) | 0.9774 (4) | 0.4826 (3) | 0.032 (2) | |
H16B | 0.4510 | 0.9601 | 0.5175 | 0.038* | |
C21B | 0.4522 (5) | 0.7858 (4) | 0.3966 (3) | 0.021 (2) | |
C22B | 0.5061 (6) | 0.7556 (4) | 0.3594 (4) | 0.036 (2) | |
H22B | 0.5634 | 0.7643 | 0.3623 | 0.044* | |
C23B | 0.4762 (6) | 0.7139 (5) | 0.3178 (3) | 0.038 (2) | |
H23B | 0.5139 | 0.6926 | 0.2937 | 0.045* | |
C24B | 0.3937 (6) | 0.7024 (4) | 0.3113 (4) | 0.039 (2) | |
H24B | 0.3740 | 0.6757 | 0.2818 | 0.047* | |
C25B | 0.3393 (6) | 0.7316 (4) | 0.3481 (4) | 0.035 (2) | |
H25B | 0.2821 | 0.7226 | 0.3447 | 0.042* | |
C26B | 0.3675 (5) | 0.7725 (4) | 0.3907 (3) | 0.033 (2) | |
H26B | 0.3296 | 0.7920 | 0.4155 | 0.039* | |
C31B | 0.5982 (5) | 0.7822 (4) | 0.5971 (4) | 0.028 (2) | |
C32B | 0.5809 (5) | 0.7407 (5) | 0.6416 (3) | 0.031 (2) | |
H32B | 0.5672 | 0.6909 | 0.6373 | 0.038* | |
C33B | 0.5850 (5) | 0.7707 (5) | 0.6915 (4) | 0.039 (2) | |
H33B | 0.5727 | 0.7416 | 0.7215 | 0.046* | |
C34B | 0.6054 (6) | 0.8438 (5) | 0.6981 (4) | 0.050 (3) | |
H34B | 0.6083 | 0.8650 | 0.7322 | 0.060* | |
C35B | 0.6225 (6) | 0.8844 (5) | 0.6535 (4) | 0.049 (3) | |
H35B | 0.6352 | 0.9345 | 0.6575 | 0.059* | |
C36B | 0.6192 (6) | 0.8548 (5) | 0.6036 (4) | 0.044 (3) | |
H36B | 0.6334 | 0.8835 | 0.5737 | 0.052* | |
C41B | 0.6349 (4) | 0.6585 (4) | 0.5264 (4) | 0.025 (2) | |
C42B | 0.6209 (5) | 0.6187 (4) | 0.4799 (3) | 0.031 (2) | |
H42B | 0.5850 | 0.6377 | 0.4537 | 0.037* | |
C43B | 0.6584 (5) | 0.5518 (4) | 0.4710 (4) | 0.041 (2) | |
H43B | 0.6487 | 0.5253 | 0.4395 | 0.049* | |
C44B | 0.7106 (5) | 0.5249 (5) | 0.5093 (4) | 0.039 (2) | |
H44B | 0.7359 | 0.4790 | 0.5040 | 0.047* | |
C45B | 0.7249 (5) | 0.5638 (5) | 0.5553 (4) | 0.037 (2) | |
H45B | 0.7620 | 0.5446 | 0.5807 | 0.044* | |
C46B | 0.6880 (5) | 0.6298 (4) | 0.5642 (4) | 0.028 (2) | |
H46B | 0.6978 | 0.6554 | 0.5961 | 0.034* | |
C3B | 0.6656 (5) | 0.9702 (4) | 0.2651 (4) | 0.065 (3) | |
D3B | 0.6852 | 0.9434 | 0.2971 | 0.078* | |
Cl3B | 0.5802 (2) | 1.02738 (19) | 0.28171 (15) | 0.0795 (12) | 0.85 |
Cl4B | 0.7423 (3) | 1.0283 (2) | 0.2431 (2) | 0.1020 (15) | 0.85 |
Cl5B | 0.6342 (2) | 0.90924 (17) | 0.21743 (14) | 0.0725 (11) | 0.85 |
Cl3D | 0.7387 (17) | 0.9343 (18) | 0.2193 (11) | 0.158 (13)* | 0.15 |
Cl4D | 0.7170 (14) | 1.0502 (8) | 0.2781 (10) | 0.079 (7)* | 0.15 |
Cl5D | 0.5769 (13) | 0.9255 (16) | 0.2477 (13) | 0.133 (11)* | 0.15 |
C4B | 0.7732 (5) | 0.7494 (5) | 0.3494 (3) | 0.039 (2) | |
D4B | 0.7649 | 0.7903 | 0.3749 | 0.047* | |
Cl6B | 0.73056 (19) | 0.77430 (19) | 0.28889 (11) | 0.0869 (11) | |
Cl7B | 0.87893 (15) | 0.73303 (14) | 0.34332 (10) | 0.0475 (7) | |
Cl8B | 0.72474 (18) | 0.67132 (16) | 0.37448 (16) | 0.0984 (12) | |
C5B | 0.9365 (7) | 0.9888 (7) | 0.3462 (5) | 0.081 (4) | |
D5B | 0.9224 | 1.0414 | 0.3419 | 0.097* | |
Cl9B | 1.0258 (2) | 0.9822 (3) | 0.38697 (16) | 0.1185 (14) | |
Cl0B | 0.9561 (3) | 0.9523 (4) | 0.28601 (16) | 0.166 (2) | |
Cl11 | 0.85520 (19) | 0.94543 (17) | 0.37876 (14) | 0.0853 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
PdA | 0.0153 (3) | 0.0239 (3) | 0.0250 (4) | 0.0000 (3) | 0.0000 (3) | −0.0003 (4) |
Cl1A | 0.0162 (12) | 0.0388 (12) | 0.0454 (16) | 0.0021 (9) | −0.0027 (10) | −0.0004 (10) |
Cl2A | 0.0333 (14) | 0.0343 (12) | 0.0309 (14) | −0.0004 (10) | 0.0064 (11) | 0.0045 (11) |
P1A | 0.0157 (13) | 0.0259 (12) | 0.0270 (15) | 0.0025 (9) | 0.0010 (10) | −0.0014 (10) |
P2A | 0.0170 (12) | 0.0244 (10) | 0.0291 (13) | 0.0006 (9) | 0.0025 (11) | 0.0009 (11) |
C1A | 0.014 (4) | 0.030 (4) | 0.024 (5) | 0.002 (4) | −0.003 (3) | −0.002 (4) |
C2A | 0.019 (5) | 0.029 (4) | 0.031 (5) | −0.007 (3) | −0.003 (4) | 0.006 (4) |
C11A | 0.025 (6) | 0.027 (5) | 0.038 (6) | −0.003 (4) | 0.001 (5) | −0.011 (4) |
C12A | 0.053 (7) | 0.025 (5) | 0.023 (6) | 0.006 (4) | −0.008 (5) | 0.003 (4) |
C13A | 0.057 (7) | 0.037 (6) | 0.040 (7) | 0.006 (5) | −0.010 (5) | 0.003 (5) |
C14A | 0.040 (7) | 0.018 (5) | 0.057 (7) | 0.008 (4) | −0.020 (5) | 0.004 (5) |
C15A | 0.019 (5) | 0.030 (5) | 0.063 (7) | 0.000 (4) | −0.009 (5) | −0.005 (5) |
C16A | 0.023 (5) | 0.031 (5) | 0.028 (6) | −0.003 (4) | 0.005 (4) | 0.003 (4) |
C21A | 0.023 (5) | 0.032 (5) | 0.013 (5) | 0.001 (4) | −0.002 (4) | 0.003 (4) |
C22A | 0.027 (6) | 0.047 (6) | 0.032 (6) | 0.004 (5) | 0.006 (4) | −0.003 (5) |
C23A | 0.039 (6) | 0.051 (6) | 0.034 (6) | 0.006 (5) | −0.003 (5) | −0.017 (5) |
C24A | 0.031 (6) | 0.037 (5) | 0.024 (6) | −0.007 (4) | −0.001 (4) | 0.000 (4) |
C25A | 0.031 (6) | 0.036 (5) | 0.032 (6) | −0.014 (4) | −0.004 (4) | 0.000 (4) |
C26A | 0.019 (5) | 0.040 (5) | 0.037 (6) | 0.001 (4) | −0.003 (4) | 0.002 (4) |
C31A | 0.024 (6) | 0.026 (5) | 0.036 (6) | 0.014 (4) | −0.002 (4) | −0.005 (4) |
C32A | 0.031 (6) | 0.045 (5) | 0.025 (6) | 0.001 (4) | −0.005 (4) | −0.001 (5) |
C33A | 0.037 (6) | 0.075 (7) | 0.019 (6) | −0.001 (6) | −0.008 (5) | 0.013 (5) |
C34A | 0.050 (7) | 0.064 (7) | 0.033 (7) | 0.002 (6) | −0.009 (6) | −0.014 (5) |
C35A | 0.049 (7) | 0.051 (6) | 0.041 (7) | −0.013 (5) | −0.007 (5) | −0.010 (6) |
C36A | 0.038 (6) | 0.026 (5) | 0.037 (6) | 0.006 (4) | 0.004 (5) | 0.012 (4) |
C41A | 0.015 (4) | 0.014 (4) | 0.039 (6) | 0.004 (3) | 0.005 (5) | −0.001 (4) |
C42A | 0.033 (6) | 0.036 (5) | 0.040 (6) | 0.002 (4) | 0.011 (4) | 0.002 (4) |
C43A | 0.044 (7) | 0.032 (6) | 0.078 (9) | −0.007 (5) | 0.009 (6) | −0.018 (5) |
C44A | 0.024 (6) | 0.022 (5) | 0.099 (9) | 0.001 (4) | 0.020 (6) | −0.012 (6) |
C45A | 0.023 (6) | 0.036 (6) | 0.074 (8) | −0.003 (5) | −0.009 (5) | 0.021 (5) |
C46A | 0.016 (5) | 0.025 (5) | 0.059 (7) | −0.006 (4) | 0.001 (5) | 0.006 (4) |
C3A | 0.026 (6) | 0.045 (5) | 0.040 (6) | −0.006 (4) | 0.007 (4) | 0.005 (5) |
Cl3A | 0.066 (2) | 0.081 (2) | 0.0365 (16) | 0.0040 (16) | 0.0094 (14) | 0.0071 (15) |
Cl4A | 0.101 (3) | 0.0504 (16) | 0.071 (2) | −0.0013 (17) | 0.0017 (18) | −0.0047 (15) |
Cl5A | 0.0573 (19) | 0.079 (2) | 0.0556 (19) | −0.0134 (16) | −0.0064 (15) | 0.0042 (16) |
C4A | 0.023 (6) | 0.060 (6) | 0.041 (6) | −0.001 (5) | 0.009 (5) | −0.014 (5) |
Cl6A | 0.0395 (16) | 0.0642 (17) | 0.0510 (17) | 0.0045 (13) | −0.0082 (13) | −0.0128 (14) |
Cl7A | 0.0289 (15) | 0.088 (2) | 0.0465 (17) | 0.0027 (13) | −0.0035 (12) | −0.0014 (14) |
Cl8A | 0.077 (2) | 0.081 (2) | 0.087 (2) | −0.0137 (18) | 0.027 (2) | 0.0193 (19) |
C5A | 0.039 (7) | 0.051 (6) | 0.045 (7) | 0.010 (5) | −0.003 (5) | −0.011 (5) |
Cl9A | 0.0369 (17) | 0.0600 (16) | 0.0606 (18) | 0.0089 (13) | −0.0080 (14) | 0.0032 (14) |
Cl0A | 0.059 (2) | 0.121 (3) | 0.061 (2) | −0.0155 (19) | 0.0016 (17) | −0.0333 (19) |
Cl10 | 0.098 (3) | 0.064 (2) | 0.151 (4) | 0.038 (2) | −0.051 (3) | −0.011 (2) |
PdB | 0.0162 (4) | 0.0235 (3) | 0.0262 (4) | −0.0008 (3) | −0.0001 (3) | −0.0004 (4) |
Cl1B | 0.0139 (12) | 0.0396 (13) | 0.0556 (15) | −0.0017 (10) | −0.0055 (10) | 0.0037 (11) |
Cl2B | 0.0328 (13) | 0.0322 (11) | 0.0305 (13) | −0.0018 (10) | 0.0093 (11) | 0.0025 (10) |
P1B | 0.0200 (13) | 0.0246 (12) | 0.0225 (14) | 0.0016 (9) | 0.0007 (9) | −0.0001 (9) |
P2B | 0.0175 (12) | 0.0262 (11) | 0.0280 (13) | −0.0011 (9) | −0.0026 (11) | 0.0027 (12) |
C1B | 0.023 (5) | 0.030 (5) | 0.020 (5) | −0.005 (4) | 0.006 (4) | −0.001 (4) |
C2B | 0.024 (5) | 0.022 (4) | 0.031 (6) | −0.004 (3) | −0.001 (4) | 0.005 (4) |
C11B | 0.013 (5) | 0.020 (4) | 0.037 (6) | −0.001 (4) | 0.003 (4) | 0.004 (4) |
C12B | 0.034 (6) | 0.026 (5) | 0.026 (6) | −0.004 (4) | 0.006 (4) | −0.005 (4) |
C13B | 0.037 (6) | 0.035 (5) | 0.031 (6) | −0.002 (4) | −0.001 (5) | 0.010 (5) |
C14B | 0.030 (6) | 0.027 (5) | 0.049 (7) | 0.005 (4) | 0.007 (5) | −0.004 (5) |
C15B | 0.038 (6) | 0.021 (4) | 0.038 (7) | 0.000 (4) | 0.005 (5) | −0.002 (4) |
C16B | 0.030 (5) | 0.028 (5) | 0.037 (6) | 0.007 (4) | 0.000 (4) | −0.002 (4) |
C21B | 0.024 (5) | 0.021 (4) | 0.019 (5) | −0.008 (4) | −0.001 (4) | 0.000 (4) |
C22B | 0.035 (6) | 0.035 (5) | 0.039 (6) | 0.004 (4) | 0.005 (5) | −0.003 (5) |
C23B | 0.043 (7) | 0.051 (6) | 0.019 (6) | 0.005 (5) | 0.006 (5) | −0.006 (4) |
C24B | 0.041 (7) | 0.041 (6) | 0.035 (6) | 0.006 (5) | −0.010 (5) | −0.012 (4) |
C25B | 0.029 (6) | 0.030 (5) | 0.047 (7) | 0.000 (4) | −0.013 (5) | 0.005 (5) |
C26B | 0.034 (6) | 0.030 (5) | 0.034 (6) | −0.002 (4) | −0.005 (5) | −0.002 (4) |
C31B | 0.012 (5) | 0.029 (5) | 0.042 (6) | 0.005 (4) | −0.007 (4) | 0.003 (4) |
C32B | 0.020 (5) | 0.041 (5) | 0.034 (6) | −0.001 (4) | 0.000 (4) | −0.002 (5) |
C33B | 0.032 (6) | 0.051 (6) | 0.033 (6) | 0.000 (5) | −0.003 (5) | −0.007 (5) |
C34B | 0.057 (7) | 0.058 (7) | 0.035 (7) | 0.002 (5) | −0.014 (6) | −0.008 (5) |
C35B | 0.057 (8) | 0.042 (6) | 0.050 (7) | 0.005 (5) | −0.024 (6) | −0.009 (6) |
C36B | 0.054 (7) | 0.042 (6) | 0.035 (7) | 0.011 (5) | −0.006 (5) | −0.005 (5) |
C41B | 0.012 (5) | 0.029 (5) | 0.035 (6) | −0.002 (3) | −0.003 (4) | 0.005 (4) |
C42B | 0.020 (5) | 0.040 (5) | 0.032 (6) | −0.008 (4) | −0.004 (4) | 0.003 (4) |
C43B | 0.036 (6) | 0.025 (5) | 0.061 (7) | −0.006 (4) | −0.003 (6) | −0.008 (5) |
C44B | 0.026 (6) | 0.036 (5) | 0.056 (7) | 0.005 (5) | 0.004 (5) | 0.005 (5) |
C45B | 0.021 (6) | 0.046 (6) | 0.043 (6) | 0.001 (5) | −0.006 (5) | 0.008 (5) |
C46B | 0.019 (5) | 0.032 (5) | 0.034 (6) | −0.007 (4) | 0.004 (4) | 0.004 (4) |
C3B | 0.088 (9) | 0.076 (8) | 0.031 (7) | −0.005 (7) | 0.016 (6) | 0.009 (6) |
Cl3B | 0.078 (3) | 0.072 (2) | 0.089 (3) | 0.017 (2) | 0.026 (2) | 0.006 (2) |
Cl4B | 0.077 (3) | 0.105 (3) | 0.124 (4) | −0.032 (3) | 0.021 (3) | 0.001 (3) |
Cl5B | 0.077 (3) | 0.063 (2) | 0.077 (3) | 0.012 (2) | −0.027 (2) | −0.0090 (19) |
C4B | 0.024 (6) | 0.057 (6) | 0.036 (6) | 0.007 (5) | 0.002 (4) | −0.010 (5) |
Cl6B | 0.069 (2) | 0.142 (3) | 0.050 (2) | 0.056 (2) | −0.0174 (16) | −0.0237 (19) |
Cl7B | 0.0300 (14) | 0.0698 (17) | 0.0426 (16) | 0.0054 (13) | −0.0012 (12) | −0.0038 (13) |
Cl8B | 0.056 (2) | 0.0531 (18) | 0.186 (4) | −0.0014 (17) | 0.047 (2) | 0.007 (2) |
C5B | 0.063 (9) | 0.083 (9) | 0.096 (11) | 0.001 (7) | 0.019 (8) | 0.015 (8) |
Cl9B | 0.047 (2) | 0.186 (4) | 0.122 (3) | −0.010 (3) | 0.006 (2) | −0.024 (3) |
Cl0B | 0.106 (4) | 0.315 (7) | 0.079 (3) | 0.039 (4) | 0.022 (3) | −0.006 (4) |
Cl11 | 0.062 (2) | 0.086 (2) | 0.108 (3) | −0.0212 (18) | 0.026 (2) | −0.010 (2) |
PdA—P1A | 2.254 (2) | PdB—Cl1B | 2.365 (2) |
PdA—P2A | 2.236 (2) | PdB—Cl2B | 2.367 (2) |
PdA—Cl1A | 2.363 (2) | P1B—C1B | 1.841 (7) |
PdA—Cl2A | 2.361 (2) | P1B—C11B | 1.820 (8) |
P1A—C1A | 1.840 (7) | P1B—C21B | 1.810 (8) |
P1A—C11A | 1.815 (8) | P2B—C2B | 1.846 (7) |
P1A—C21A | 1.818 (8) | P2B—C31B | 1.818 (9) |
P2A—C2A | 1.816 (7) | P2B—C41B | 1.813 (7) |
P2A—C31A | 1.811 (9) | C1B—C2B | 1.546 (10) |
P2A—C41A | 1.818 (7) | C11B—C16B | 1.375 (10) |
C1A—C2A | 1.522 (10) | C11B—C12B | 1.389 (11) |
C11A—C12A | 1.393 (11) | C12B—C13B | 1.383 (11) |
C11A—C16A | 1.406 (10) | C13B—C14B | 1.392 (11) |
C12A—C13A | 1.382 (11) | C14B—C15B | 1.376 (11) |
C13A—C14A | 1.411 (12) | C15B—C16B | 1.384 (10) |
C14A—C15A | 1.373 (12) | C21B—C22B | 1.403 (11) |
C15A—C16A | 1.392 (10) | C21B—C26B | 1.409 (11) |
C21A—C22A | 1.393 (11) | C22B—C23B | 1.392 (11) |
C21A—C26A | 1.407 (11) | C23B—C24B | 1.370 (11) |
C22A—C23A | 1.404 (11) | C24B—C25B | 1.394 (12) |
C23A—C24A | 1.363 (11) | C25B—C26B | 1.393 (11) |
C24A—C25A | 1.399 (11) | C31B—C36B | 1.388 (11) |
C25A—C26A | 1.382 (11) | C31B—C32B | 1.389 (11) |
C31A—C32A | 1.397 (11) | C32B—C33B | 1.382 (11) |
C31A—C36A | 1.412 (11) | C33B—C34B | 1.395 (12) |
C32A—C33A | 1.382 (12) | C34B—C35B | 1.383 (12) |
C33A—C34A | 1.375 (12) | C35B—C36B | 1.377 (12) |
C34A—C35A | 1.363 (13) | C41B—C46B | 1.394 (11) |
C35A—C36A | 1.380 (12) | C41B—C42B | 1.405 (11) |
C41A—C46A | 1.390 (11) | C42B—C43B | 1.392 (11) |
C41A—C42A | 1.406 (11) | C43B—C44B | 1.381 (12) |
C42A—C43A | 1.384 (11) | C44B—C45B | 1.387 (11) |
C43A—C44A | 1.386 (13) | C45B—C46B | 1.374 (11) |
C44A—C45A | 1.369 (13) | C3B—Cl5D | 1.721 (10) |
C45A—C46A | 1.388 (11) | C3B—Cl4D | 1.725 (10) |
C3A—Cl4A | 1.746 (9) | C3B—Cl5B | 1.726 (7) |
C3A—Cl3A | 1.774 (9) | C3B—Cl4B | 1.737 (7) |
C3A—Cl5A | 1.770 (9) | C3B—Cl3D | 1.789 (10) |
C4A—Cl8A | 1.746 (9) | C3B—Cl3B | 1.793 (7) |
C4A—Cl6A | 1.741 (10) | C4B—Cl6B | 1.744 (9) |
C4A—Cl7A | 1.790 (9) | C4B—Cl7B | 1.755 (9) |
C5A—Cl10 | 1.709 (9) | C4B—Cl8B | 1.759 (9) |
C5A—Cl0A | 1.725 (9) | C5B—Cl0B | 1.696 (12) |
C5A—Cl9A | 1.800 (9) | C5B—Cl11 | 1.752 (11) |
PdB—P1B | 2.238 (2) | C5B—Cl9B | 1.789 (12) |
PdB—P2B | 2.238 (2) | ||
P2A—PdA—P1A | 85.63 (8) | C21B—P1B—C11B | 106.0 (4) |
P2A—PdA—Cl2A | 176.27 (8) | C21B—P1B—C1B | 105.7 (4) |
P1A—PdA—Cl2A | 92.98 (8) | C11B—P1B—C1B | 107.2 (4) |
P2A—PdA—Cl1A | 89.68 (8) | C21B—P1B—PdB | 113.0 (3) |
P1A—PdA—Cl1A | 175.26 (8) | C11B—P1B—PdB | 116.6 (3) |
Cl2A—PdA—Cl1A | 91.74 (8) | C1B—P1B—PdB | 107.7 (3) |
C21A—P1A—C11A | 104.4 (4) | C41B—P2B—C31B | 109.1 (4) |
C21A—P1A—C1A | 106.6 (4) | C41B—P2B—C2B | 106.6 (3) |
C11A—P1A—C1A | 106.6 (4) | C31B—P2B—C2B | 103.6 (4) |
C21A—P1A—PdA | 110.6 (3) | C41B—P2B—PdB | 113.7 (3) |
C11A—P1A—PdA | 121.0 (3) | C31B—P2B—PdB | 114.3 (3) |
C1A—P1A—PdA | 106.8 (2) | C2B—P2B—PdB | 108.7 (3) |
C31A—P2A—C2A | 104.6 (4) | C2B—C1B—P1B | 106.9 (5) |
C31A—P2A—C41A | 108.1 (4) | C1B—C2B—P2B | 107.2 (5) |
C2A—P2A—C41A | 104.7 (3) | C16B—C11B—C12B | 118.8 (7) |
C31A—P2A—PdA | 113.7 (3) | C16B—C11B—P1B | 120.3 (6) |
C2A—P2A—PdA | 108.4 (3) | C12B—C11B—P1B | 120.8 (6) |
C41A—P2A—PdA | 116.4 (3) | C13B—C12B—C11B | 120.6 (8) |
C2A—C1A—P1A | 107.0 (5) | C12B—C13B—C14B | 119.5 (8) |
C1A—C2A—P2A | 108.3 (5) | C15B—C14B—C13B | 120.4 (8) |
C12A—C11A—C16A | 119.9 (8) | C14B—C15B—C16B | 119.2 (8) |
C12A—C11A—P1A | 119.7 (6) | C11B—C16B—C15B | 121.6 (8) |
C16A—C11A—P1A | 120.2 (7) | C22B—C21B—C26B | 118.3 (8) |
C13A—C12A—C11A | 119.8 (8) | C22B—C21B—P1B | 121.5 (6) |
C12A—C13A—C14A | 120.0 (9) | C26B—C21B—P1B | 120.2 (6) |
C15A—C14A—C13A | 120.4 (8) | C23B—C22B—C21B | 120.5 (8) |
C14A—C15A—C16A | 119.9 (9) | C24B—C23B—C22B | 121.2 (8) |
C15A—C16A—C11A | 120.0 (8) | C23B—C24B—C25B | 119.0 (9) |
C22A—C21A—C26A | 119.2 (8) | C26B—C25B—C24B | 121.1 (9) |
C22A—C21A—P1A | 121.1 (7) | C25B—C26B—C21B | 119.9 (8) |
C26A—C21A—P1A | 119.7 (6) | C36B—C31B—C32B | 119.0 (9) |
C21A—C22A—C23A | 119.5 (8) | C36B—C31B—P2B | 118.8 (7) |
C24A—C23A—C22A | 121.0 (8) | C32B—C31B—P2B | 122.0 (6) |
C23A—C24A—C25A | 120.0 (8) | C33B—C32B—C31B | 120.7 (8) |
C26A—C25A—C24A | 119.9 (8) | C32B—C33B—C34B | 120.4 (10) |
C25A—C26A—C21A | 120.4 (8) | C35B—C34B—C33B | 118.2 (9) |
C32A—C31A—C36A | 117.2 (8) | C36B—C35B—C34B | 121.8 (9) |
C32A—C31A—P2A | 122.1 (7) | C35B—C36B—C31B | 119.9 (10) |
C36A—C31A—P2A | 120.6 (7) | C46B—C41B—C42B | 118.6 (7) |
C33A—C32A—C31A | 120.9 (9) | C46B—C41B—P2B | 124.9 (7) |
C34A—C33A—C32A | 120.7 (9) | C42B—C41B—P2B | 116.4 (6) |
C35A—C34A—C33A | 119.6 (10) | C43B—C42B—C41B | 121.6 (8) |
C34A—C35A—C36A | 121.1 (9) | C44B—C43B—C42B | 118.3 (9) |
C35A—C36A—C31A | 120.5 (9) | C43B—C44B—C45B | 120.5 (9) |
C46A—C41A—C42A | 119.6 (7) | C46B—C45B—C44B | 121.3 (9) |
C46A—C41A—P2A | 123.2 (7) | C45B—C46B—C41B | 119.6 (8) |
C42A—C41A—P2A | 117.1 (6) | Cl5D—C3B—Cl4D | 149.8 (15) |
C43A—C42A—C41A | 120.3 (9) | Cl5D—C3B—Cl5B | 42.3 (11) |
C44A—C43A—C42A | 119.8 (9) | Cl4D—C3B—Cl5B | 146.3 (10) |
C45A—C44A—C43A | 119.6 (8) | Cl5D—C3B—Cl4B | 144.7 (13) |
C44A—C45A—C46A | 122.1 (9) | Cl4D—C3B—Cl4B | 35.6 (8) |
C41A—C46A—C45A | 118.5 (9) | Cl5B—C3B—Cl4B | 112.9 (5) |
Cl4A—C3A—Cl3A | 110.3 (5) | Cl5D—C3B—Cl3D | 102.5 (17) |
Cl4A—C3A—Cl5A | 111.2 (5) | Cl4D—C3B—Cl3D | 96.6 (14) |
Cl3A—C3A—Cl5A | 109.4 (5) | Cl5B—C3B—Cl3D | 60.2 (12) |
Cl8A—C4A—Cl6A | 112.0 (5) | Cl4B—C3B—Cl3D | 62.6 (11) |
Cl8A—C4A—Cl7A | 108.9 (5) | Cl5D—C3B—Cl3B | 71.9 (12) |
Cl6A—C4A—Cl7A | 110.5 (5) | Cl4D—C3B—Cl3B | 80.3 (9) |
Cl10—C5A—Cl0A | 113.1 (6) | Cl5B—C3B—Cl3B | 108.4 (5) |
Cl10—C5A—Cl9A | 109.7 (5) | Cl4B—C3B—Cl3B | 105.8 (5) |
Cl0A—C5A—Cl9A | 109.0 (5) | Cl3D—C3B—Cl3B | 152.2 (13) |
P2B—PdB—P1B | 85.77 (8) | Cl6B—C4B—Cl7B | 111.0 (5) |
P2B—PdB—Cl1B | 90.47 (8) | Cl6B—C4B—Cl8B | 110.6 (5) |
P1B—PdB—Cl1B | 174.30 (8) | Cl7B—C4B—Cl8B | 109.4 (5) |
P2B—PdB—Cl2B | 173.73 (8) | Cl0B—C5B—Cl11 | 112.6 (7) |
P1B—PdB—Cl2B | 90.45 (8) | Cl0B—C5B—Cl9B | 109.7 (7) |
Cl1B—PdB—Cl2B | 93.66 (8) | Cl11—C5B—Cl9B | 108.2 (7) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3A—D3A···Cl2A | 1.00 | 2.62 | 3.452 (9) | 141 |
C4A—D4A···Cl1A | 1.00 | 2.81 | 3.649 (10) | 141 |
C4A—D4A···Cl2A | 1.00 | 2.88 | 3.717 (9) | 142 |
C5A—D5A···Cl2A | 1.00 | 2.76 | 3.534 (10) | 135 |
C3B—D3B···Cl2B | 1.00 | 2.61 | 3.501 (10) | 148 |
C4B—D4B···Cl1B | 1.00 | 2.96 | 3.759 (9) | 137 |
C4B—D4B···Cl2B | 1.00 | 2.70 | 3.513 (9) | 138 |
C5B—D5B···Cl7Ai | 1.00 | 2.98 | 3.967 (13) | 170 |
Symmetry code: (i) x, y+1, z. |
Experimental details
Crystal data | |
Chemical formula | C26H24Cl2P2Pd·3(CCl3D) |
Mr | 936.81 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 16.292 (1), 18.404 (1), 25.317 (2) |
V (Å3) | 7591 (1) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.34 × 0.25 × 0.08 |
Data collection | |
Diffractometer | SMART 1K CCD area detector diffractometer |
Absorption correction | Integration XPREP SHELXTL (Siemens, 1995b) |
Tmin, Tmax | 0.701, 0.920 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 41687, 12994, 9802 |
Rint | 0.083 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.099, 1.78 |
No. of reflections | 12994 |
No. of parameters | 787 |
No. of restraints | 15 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.36, −0.98 |
Absolute structure | Flack (1983) |
Absolute structure parameter | −0.02 (3) |
Computer programs: SMART (Siemens, 1995a), SAINT (Siemens, 1995a), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), SHELXTL (Siemens, 1995b).
PdA—P1A | 2.254 (2) | PdB—P1B | 2.238 (2) |
PdA—P2A | 2.236 (2) | PdB—P2B | 2.238 (2) |
PdA—Cl1A | 2.363 (2) | PdB—Cl1B | 2.365 (2) |
PdA—Cl2A | 2.361 (2) | PdB—Cl2B | 2.367 (2) |
P1A—C1A | 1.840 (7) | P1B—C1B | 1.841 (7) |
P1A—C11A | 1.815 (8) | P1B—C11B | 1.820 (8) |
P1A—C21A | 1.818 (8) | P1B—C21B | 1.810 (8) |
P2A—C2A | 1.816 (7) | P2B—C2B | 1.846 (7) |
P2A—C31A | 1.811 (9) | P2B—C31B | 1.818 (9) |
P2A—C41A | 1.818 (7) | P2B—C41B | 1.813 (7) |
P2A—PdA—P1A | 85.63 (8) | P2B—PdB—P1B | 85.77 (8) |
P2A—PdA—Cl2A | 176.27 (8) | P2B—PdB—Cl1B | 90.47 (8) |
P1A—PdA—Cl2A | 92.98 (8) | P1B—PdB—Cl1B | 174.30 (8) |
P2A—PdA—Cl1A | 89.68 (8) | P2B—PdB—Cl2B | 173.73 (8) |
P1A—PdA—Cl1A | 175.26 (8) | P1B—PdB—Cl2B | 90.45 (8) |
Cl2A—PdA—Cl1A | 91.74 (8) | Cl1B—PdB—Cl2B | 93.66 (8) |
C21A—P1A—C11A | 104.4 (4) | C21B—P1B—C11B | 106.0 (4) |
C21A—P1A—C1A | 106.6 (4) | C21B—P1B—C1B | 105.7 (4) |
C11A—P1A—C1A | 106.6 (4) | C11B—P1B—C1B | 107.2 (4) |
C21A—P1A—PdA | 110.6 (3) | C21B—P1B—PdB | 113.0 (3) |
C11A—P1A—PdA | 121.0 (3) | C11B—P1B—PdB | 116.6 (3) |
C1A—P1A—PdA | 106.8 (2) | C1B—P1B—PdB | 107.7 (3) |
C31A—P2A—C2A | 104.6 (4) | C41B—P2B—C31B | 109.1 (4) |
C31A—P2A—C41A | 108.1 (4) | C41B—P2B—C2B | 106.6 (3) |
C2A—P2A—C41A | 104.7 (3) | C31B—P2B—C2B | 103.6 (4) |
C31A—P2A—PdA | 113.7 (3) | C41B—P2B—PdB | 113.7 (3) |
C2A—P2A—PdA | 108.4 (3) | C31B—P2B—PdB | 114.3 (3) |
C41A—P2A—PdA | 116.4 (3) | C2B—P2B—PdB | 108.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
C3A—D3A···Cl2A | 1.00 | 2.62 | 3.452 (9) | 141.1 |
C4A—D4A···Cl1A | 1.00 | 2.81 | 3.649 (10) | 141.4 |
C4A—D4A···Cl2A | 1.00 | 2.88 | 3.717 (9) | 142.1 |
C5A—D5A···Cl2A | 1.00 | 2.76 | 3.534 (10) | 134.8 |
C3B—D3B···Cl2B | 1.00 | 2.61 | 3.501 (10) | 148.1 |
C4B—D4B···Cl1B | 1.00 | 2.96 | 3.759 (9) | 137.1 |
C4B—D4B···Cl2B | 1.00 | 2.70 | 3.513 (9) | 138.3 |
C5B—D5B···Cl7Ai | 1.00 | 2.98 | 3.967 (13) | 170.1 |
Symmetry code: (i) x, y+1, z. |
[PdCl2(dppe)] (I) was first studied crystallographically by Steffen & Palenik (1976) in the form of its 1:1 solvate with CH2Cl2 (II). Later, Singh et al. (1995) determined the crystal structure of pure (I). In the course of our studies of organopalladium phosphine complexes we found that re-crystallization of (I) from deuterochloroform gives a stable 1:3 solvate [PdCl2(dppe)].3 CDCl3 (III), the structure of which is reported herein.
The asymmetric unit of (III) comprises two [PdCl2(dppe)] molecules (A and B) and six molecules of deuterochloroform (Fig. 1). The [PdCl2(dppe)] molecules are related to each other by an approximate translation of b/2. Atoms, related by this pseudo-translation, are given the same numbers with letters A or B added. The Pd atoms deviate from the ideal b/2 translation by 0.54 Å, P by 0.50 and 0.56 Å, Cl by 0.62 and 0.70 Å, and C atoms by 0.09–1.10 Å with the average 0.55 Å (Fig. 2). These deviations are relatively small, compared to the length of the translation (b/2 = 9.2 Å). The [PdCl2(dppe)] molecule A has three molecules of deuterochloroform attached to it through C—D···Cl—Pd hydrogen bonds. Two of these molecules, A1 and A3 (see Fig. 1), are hydrogen-bonded to the chloride ligand Cl2A, while molecule A2 forms a bifurcated hydrogen bond with both Cl1A and Cl2A. The positions of deuterochloroform molecules B1, B2 and B3 are roughly related respectively to those of A1, A2 and A3. Molecule B2 also forms a bifurcated hydrogen bond, with Cl1B and Cl2B. Molecule B1 is hydrogen-bonded to Cl2B, but unlike A1, molecule B1 is disordered (see below). In molecule B3, the C5B, Cl9B and Cl0B atoms are related by pseudo-translation to the C5A, Cl9A and Cl0A of molecule A3, but Cl11 is not related to Cl10. Thus B3 can be described as a pseudo-equivalent of A3 with the deuterium and Cl11 atoms `swapped'. Consequently, the deuterium atom of B3 does not point towards the [PdCl2(dppe)] molecule B, but instead forms a weak hydrogen bond with the Cl7A atom of the A2 molecule, related to the original one by the crystallographic translation b.
Thus structure (III) has an (a, b/2, c) subcell, which is manifested in the diffraction pattern: reflections with k indices even, have intensities on average twice as high as those with k odd. The crystal packing can be described as a clathrate (host–guest complex), in which deuterochloroform molecules occupy infinite channels (parallel to the y axis) in the packing of [PdCl2(dppe)] molecules (Fig. 3).
The molecular structure of [PdCl2(dppe)] in (III) is similar to those found in structures (I) and (II). The palladium atom has a slightly distorted square-planar coordination. In molecule A, the PdA, P1A, P2A and Cl1A atoms are coplanar, while Cl2A deviates from their mean plane by 0.160 (4) Å. Probably because of this asymmetric distortion, the Pd—P bond lengths differ by 0.018 Å, or 9 s.u. In molecule B, the distortion is of tetrahedral mode: the the PdCl2 plane is twisted by 6.4 (1)° with respect to the PdP2 plane, and the Pd—P distances are identical. In any case, the distortion is probably due to steric strain in the chelating ligand, (Steffen & Palenik, 1976). In both [PdCl2(dppe)] molecules of (III) the 5-membered metallocycle adopts an asymmetric twist conformation: the C1 and C2 atoms are displaced from the PdP2 plane in opposite directions, by 0.48 (1) and -0.29 (1) Å in molecule A, 0.50 (1) and -0.28 (1) Å in molecule B.
The average Pd—P and Pd—Cl bond distances of 2.242 (7) and 2.364 (3) Å in (III) are essentially the same as in (II), viz. 2.230 (4) and 2.359 (2) Å (Steffen & Palenik, 1976).