Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801000848/ya6005sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801000848/ya6005Isup2.hkl |
CCDC reference: 159710
[PdMeCl(COD)] was prepared according to the literature (Chatt et al., 1957; Rülke et al., 1993). Crystals were obtained using the following procedure: a solution of 21 mg (0.079 mmol) of PPh3 in 5 ml of acetone was added very carefully (so as to disturb the mixture as little as possible) to a solution of 10 mg (0.037 mmol) of [PdMeCl(COD)] in 5 ml of acetone. Light yellow prisms of the title compound soon precipitated from the reaction mixture and were collected by filtration in an almost quantitative yield. 1H NMR (CDCl3): 7.65–7.76 (m, 15H), 7.30–7.45 (m, 18H), -0.035 (t, 3H, 3JP—H = 12.5 Hz) p.p.m. 31P NMR (CDCl3) 31.2 p.p.m.
The data were collected on a Siemens SMART CCD diffractometer using an exposure time of 20 s per frame. A total of 1890 frames were collected with a frame width of 0.25° being used.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg 1997); software used to prepare material for publication: SHELXL97.
Fig. 1. The structure of (I) showing the atom-numbering scheme and 30% probability displacement ellipsoids. H atoms are of arbitrary size. |
[PdCl(CH3)(C18H15P)2] | F(000) = 1392 |
Mr = 681.42 | Dx = 1.428 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8068 (4) Å | Cell parameters from 5564 reflections |
b = 23.3389 (9) Å | θ = 2.2–24.4° |
c = 12.3650 (5) Å | µ = 0.80 mm−1 |
β = 111.537 (1)° | T = 293 K |
V = 3169.4 (2) Å3 | Prism, light yellow |
Z = 4 | 0.37 × 0.24 × 0.11 mm |
Siemens SMART CCD diffractometer | 9837 independent reflections |
Radiation source: fine-focus sealed tube | 4925 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.076 |
ω scans | θmax = 31.7°, θmin = 1.7° |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | h = −17→17 |
Tmin = 0.621, Tmax = 0.735 | k = −34→32 |
32413 measured reflections | l = −18→18 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0243P)2] where P = (Fo2 + 2Fc2)/3 |
9837 reflections | (Δ/σ)max = 0.001 |
372 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.61 e Å−3 |
[PdCl(CH3)(C18H15P)2] | V = 3169.4 (2) Å3 |
Mr = 681.42 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 11.8068 (4) Å | µ = 0.80 mm−1 |
b = 23.3389 (9) Å | T = 293 K |
c = 12.3650 (5) Å | 0.37 × 0.24 × 0.11 mm |
β = 111.537 (1)° |
Siemens SMART CCD diffractometer | 9837 independent reflections |
Absorption correction: empirical (SADABS; Sheldrick, 1996) | 4925 reflections with I > 2σ(I) |
Tmin = 0.621, Tmax = 0.735 | Rint = 0.076 |
32413 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.071 | H-atom parameters constrained |
S = 0.85 | Δρmax = 0.43 e Å−3 |
9837 reflections | Δρmin = −0.61 e Å−3 |
372 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 | ||
Pd | 0.674140 (18) | 0.151643 (8) | −0.003725 (17) | 0.03079 (6) | |
P1 | 0.66219 (6) | 0.12867 (3) | −0.19089 (6) | 0.03063 (16) | |
P2 | 0.68079 (6) | 0.17084 (3) | 0.18281 (6) | 0.03196 (16) | |
Cl | 0.70295 (6) | 0.05093 (3) | 0.04632 (6) | 0.04242 (17) | |
C1 | 0.6652 (3) | 0.23771 (10) | −0.0404 (2) | 0.0456 (7) | |
H1A | 0.5845 | 0.2515 | −0.0539 | 0.0627 (16)* | |
H1B | 0.6842 | 0.2440 | −0.1086 | 0.0627 (16)* | |
H1C | 0.7227 | 0.2579 | 0.0241 | 0.0627 (16)* | |
C111 | 0.5315 (2) | 0.08493 (10) | −0.2759 (2) | 0.0336 (6) | |
C112 | 0.4667 (2) | 0.05369 (10) | −0.2219 (2) | 0.0406 (7) | |
H112 | 0.4899 | 0.0552 | −0.1415 | 0.0627 (16)* | |
C113 | 0.3680 (3) | 0.02045 (11) | −0.2866 (3) | 0.0510 (8) | |
H113 | 0.3255 | −0.0003 | −0.2497 | 0.0627 (16)* | |
C114 | 0.3331 (3) | 0.01806 (12) | −0.4051 (3) | 0.0587 (9) | |
H114 | 0.2661 | −0.0039 | −0.4485 | 0.0627 (16)* | |
C115 | 0.3970 (3) | 0.04822 (12) | −0.4605 (3) | 0.0597 (9) | |
H115 | 0.3740 | 0.0461 | −0.5408 | 0.0627 (16)* | |
C116 | 0.4943 (3) | 0.08121 (12) | −0.3964 (2) | 0.0474 (7) | |
H116 | 0.5366 | 0.1016 | −0.4341 | 0.0627 (16)* | |
C121 | 0.7962 (2) | 0.08767 (10) | −0.1843 (2) | 0.0327 (6) | |
C122 | 0.9025 (3) | 0.09334 (12) | −0.0894 (3) | 0.0465 (7) | |
H122 | 0.9051 | 0.1184 | −0.0301 | 0.0627 (16)* | |
C123 | 1.0055 (3) | 0.06265 (14) | −0.0801 (3) | 0.0612 (9) | |
H123 | 1.0769 | 0.0677 | −0.0158 | 0.0627 (16)* | |
C124 | 1.0025 (3) | 0.02494 (13) | −0.1651 (3) | 0.0624 (10) | |
H124 | 1.0714 | 0.0037 | −0.1586 | 0.0627 (16)* | |
C125 | 0.8976 (3) | 0.01847 (13) | −0.2602 (3) | 0.0681 (10) | |
H125 | 0.8952 | −0.0071 | −0.3186 | 0.0627 (16)* | |
C126 | 0.7953 (3) | 0.04969 (12) | −0.2698 (3) | 0.0532 (8) | |
H126 | 0.7246 | 0.0451 | −0.3351 | 0.0627 (16)* | |
C131 | 0.6534 (2) | 0.18679 (10) | −0.2936 (2) | 0.0330 (6) | |
C132 | 0.5440 (3) | 0.21571 (12) | −0.3436 (2) | 0.0489 (8) | |
H132 | 0.4779 | 0.2055 | −0.3238 | 0.0627 (16)* | |
C133 | 0.5315 (3) | 0.25947 (12) | −0.4222 (3) | 0.0563 (8) | |
H133 | 0.4571 | 0.2781 | −0.4562 | 0.0627 (16)* | |
C134 | 0.6293 (3) | 0.27534 (12) | −0.4499 (3) | 0.0561 (8) | |
H134 | 0.6214 | 0.3046 | −0.5031 | 0.0627 (16)* | |
C135 | 0.7383 (3) | 0.24815 (14) | −0.3992 (3) | 0.0649 (9) | |
H135 | 0.8049 | 0.2596 | −0.4169 | 0.0627 (16)* | |
C136 | 0.7506 (3) | 0.20355 (12) | −0.3213 (2) | 0.0501 (8) | |
H136 | 0.8251 | 0.1850 | −0.2879 | 0.0627 (16)* | |
C211 | 0.5462 (2) | 0.14533 (10) | 0.2080 (2) | 0.0337 (6) | |
C212 | 0.4735 (2) | 0.10292 (11) | 0.1360 (2) | 0.0393 (7) | |
H212 | 0.4943 | 0.0878 | 0.0762 | 0.0627 (16)* | |
C213 | 0.3705 (3) | 0.08318 (12) | 0.1529 (3) | 0.0496 (8) | |
H213 | 0.3233 | 0.0545 | 0.1054 | 0.0627 (16)* | |
C214 | 0.3383 (3) | 0.10581 (13) | 0.2392 (3) | 0.0573 (9) | |
H214 | 0.2684 | 0.0928 | 0.2495 | 0.0627 (16)* | |
C215 | 0.4078 (3) | 0.14741 (13) | 0.3105 (3) | 0.0587 (8) | |
H215 | 0.3849 | 0.1626 | 0.3689 | 0.0627 (16)* | |
C216 | 0.5124 (3) | 0.16726 (11) | 0.2967 (2) | 0.0470 (7) | |
H216 | 0.5599 | 0.1952 | 0.3465 | 0.0627 (16)* | |
C221 | 0.6981 (2) | 0.24450 (10) | 0.2373 (2) | 0.0335 (6) | |
C222 | 0.8076 (2) | 0.26523 (11) | 0.3123 (2) | 0.0436 (7) | |
H222 | 0.8749 | 0.2411 | 0.3372 | 0.0627 (16)* | |
C223 | 0.8202 (3) | 0.32128 (12) | 0.3518 (3) | 0.0566 (9) | |
H223 | 0.8956 | 0.3344 | 0.4016 | 0.0627 (16)* | |
C224 | 0.7228 (3) | 0.35707 (12) | 0.3179 (3) | 0.0544 (8) | |
H224 | 0.7311 | 0.3945 | 0.3454 | 0.0627 (16)* | |
C225 | 0.6118 (3) | 0.33783 (12) | 0.2428 (3) | 0.0550 (8) | |
H225 | 0.5447 | 0.3621 | 0.2199 | 0.0627 (16)* | |
C226 | 0.6001 (3) | 0.28208 (11) | 0.2014 (2) | 0.0464 (7) | |
H226 | 0.5254 | 0.2697 | 0.1486 | 0.0627 (16)* | |
C231 | 0.8121 (2) | 0.13695 (10) | 0.2909 (2) | 0.0363 (6) | |
C232 | 0.8135 (3) | 0.11636 (12) | 0.3959 (3) | 0.0539 (8) | |
H232 | 0.7420 | 0.1159 | 0.4112 | 0.0627 (16)* | |
C233 | 0.9202 (4) | 0.09639 (14) | 0.4786 (3) | 0.0769 (11) | |
H233 | 0.9193 | 0.0815 | 0.5481 | 0.0627 (16)* | |
C234 | 1.0267 (3) | 0.09816 (14) | 0.4599 (3) | 0.0723 (11) | |
H234 | 1.0984 | 0.0856 | 0.5172 | 0.0627 (16)* | |
C235 | 1.0282 (3) | 0.11832 (13) | 0.3573 (3) | 0.0621 (9) | |
H235 | 1.1011 | 0.1198 | 0.3446 | 0.0627 (16)* | |
C236 | 0.9213 (3) | 0.13663 (11) | 0.2715 (3) | 0.0505 (8) | |
H236 | 0.9223 | 0.1488 | 0.2003 | 0.0627 (16)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.03425 (11) | 0.03080 (10) | 0.02831 (11) | 0.00194 (10) | 0.01265 (9) | −0.00007 (9) |
P1 | 0.0328 (4) | 0.0322 (3) | 0.0282 (4) | 0.0014 (3) | 0.0127 (3) | −0.0002 (3) |
P2 | 0.0342 (4) | 0.0320 (4) | 0.0294 (4) | −0.0005 (3) | 0.0114 (3) | −0.0021 (3) |
Cl | 0.0531 (4) | 0.0350 (4) | 0.0407 (4) | 0.0076 (3) | 0.0189 (4) | 0.0041 (3) |
C1 | 0.062 (2) | 0.0344 (15) | 0.0427 (18) | 0.0010 (14) | 0.0219 (16) | −0.0005 (13) |
C111 | 0.0322 (15) | 0.0346 (14) | 0.0321 (16) | 0.0038 (11) | 0.0093 (13) | 0.0017 (12) |
C112 | 0.0437 (17) | 0.0376 (15) | 0.0407 (17) | 0.0015 (13) | 0.0157 (15) | 0.0047 (13) |
C113 | 0.0458 (19) | 0.0464 (17) | 0.058 (2) | −0.0098 (15) | 0.0165 (17) | 0.0059 (16) |
C114 | 0.049 (2) | 0.0521 (19) | 0.058 (2) | −0.0162 (15) | 0.0004 (18) | −0.0004 (16) |
C115 | 0.069 (2) | 0.063 (2) | 0.0362 (18) | −0.0165 (18) | 0.0066 (17) | −0.0015 (16) |
C116 | 0.0490 (19) | 0.0545 (18) | 0.0373 (18) | −0.0123 (15) | 0.0142 (16) | −0.0012 (14) |
C121 | 0.0361 (16) | 0.0303 (14) | 0.0336 (16) | −0.0012 (12) | 0.0152 (14) | 0.0032 (12) |
C122 | 0.0406 (18) | 0.0560 (18) | 0.0446 (19) | −0.0007 (15) | 0.0174 (16) | −0.0011 (15) |
C123 | 0.0349 (18) | 0.082 (2) | 0.067 (2) | 0.0078 (17) | 0.0185 (18) | 0.020 (2) |
C124 | 0.053 (2) | 0.052 (2) | 0.100 (3) | 0.0231 (17) | 0.048 (2) | 0.031 (2) |
C125 | 0.072 (3) | 0.051 (2) | 0.094 (3) | 0.0159 (18) | 0.046 (2) | −0.0105 (19) |
C126 | 0.0485 (19) | 0.0565 (19) | 0.053 (2) | 0.0079 (16) | 0.0167 (17) | −0.0155 (16) |
C131 | 0.0372 (16) | 0.0346 (14) | 0.0273 (15) | −0.0009 (12) | 0.0121 (13) | −0.0023 (11) |
C132 | 0.0507 (19) | 0.0491 (17) | 0.052 (2) | 0.0100 (15) | 0.0254 (17) | 0.0130 (15) |
C133 | 0.062 (2) | 0.0492 (18) | 0.058 (2) | 0.0158 (16) | 0.0219 (18) | 0.0144 (16) |
C134 | 0.072 (2) | 0.0505 (18) | 0.0431 (19) | −0.0063 (17) | 0.0179 (18) | 0.0159 (15) |
C135 | 0.057 (2) | 0.073 (2) | 0.070 (2) | −0.0088 (19) | 0.030 (2) | 0.0218 (19) |
C136 | 0.0420 (18) | 0.0576 (19) | 0.0492 (19) | 0.0010 (15) | 0.0149 (16) | 0.0125 (15) |
C211 | 0.0330 (15) | 0.0366 (14) | 0.0298 (14) | 0.0004 (12) | 0.0096 (12) | 0.0010 (12) |
C212 | 0.0375 (16) | 0.0416 (15) | 0.0391 (17) | −0.0012 (13) | 0.0143 (14) | −0.0047 (13) |
C213 | 0.0414 (18) | 0.0500 (18) | 0.056 (2) | −0.0095 (14) | 0.0156 (16) | −0.0028 (15) |
C214 | 0.049 (2) | 0.067 (2) | 0.066 (2) | −0.0050 (17) | 0.0328 (19) | 0.0073 (18) |
C215 | 0.069 (2) | 0.068 (2) | 0.057 (2) | −0.0015 (19) | 0.0448 (19) | −0.0013 (18) |
C216 | 0.0544 (19) | 0.0526 (18) | 0.0389 (17) | −0.0062 (15) | 0.0231 (16) | −0.0083 (14) |
C221 | 0.0365 (16) | 0.0346 (14) | 0.0335 (15) | 0.0018 (12) | 0.0176 (13) | −0.0008 (12) |
C222 | 0.0334 (16) | 0.0392 (16) | 0.060 (2) | −0.0028 (13) | 0.0187 (15) | −0.0081 (14) |
C223 | 0.053 (2) | 0.0437 (18) | 0.072 (2) | −0.0144 (16) | 0.0226 (19) | −0.0182 (16) |
C224 | 0.067 (2) | 0.0341 (17) | 0.072 (2) | −0.0034 (16) | 0.037 (2) | −0.0111 (15) |
C225 | 0.066 (2) | 0.0425 (18) | 0.061 (2) | 0.0185 (16) | 0.0274 (19) | 0.0072 (15) |
C226 | 0.0475 (18) | 0.0438 (17) | 0.0424 (18) | 0.0034 (14) | 0.0100 (15) | −0.0028 (14) |
C231 | 0.0400 (16) | 0.0300 (14) | 0.0341 (16) | −0.0022 (12) | 0.0080 (13) | −0.0060 (11) |
C232 | 0.051 (2) | 0.061 (2) | 0.043 (2) | −0.0087 (16) | 0.0104 (17) | 0.0067 (16) |
C233 | 0.076 (3) | 0.086 (3) | 0.046 (2) | −0.004 (2) | −0.005 (2) | 0.0202 (19) |
C234 | 0.056 (2) | 0.068 (2) | 0.063 (3) | 0.0175 (19) | −0.014 (2) | −0.0028 (19) |
C235 | 0.043 (2) | 0.059 (2) | 0.076 (3) | 0.0128 (16) | 0.011 (2) | −0.0176 (19) |
C236 | 0.0462 (19) | 0.0553 (19) | 0.0475 (19) | 0.0106 (15) | 0.0141 (16) | −0.0070 (15) |
Pd—P1 | 2.3289 (7) | C131—C136 | 1.370 (3) |
Pd—P2 | 2.3224 (7) | C132—C133 | 1.380 (4) |
Pd—Cl | 2.4227 (6) | C133—C134 | 1.371 (4) |
Pd—C1 | 2.054 (2) | C134—C135 | 1.363 (4) |
P1—C111 | 1.827 (3) | C135—C136 | 1.389 (4) |
P1—C121 | 1.825 (3) | C211—C212 | 1.396 (3) |
P1—C131 | 1.835 (2) | C211—C216 | 1.394 (3) |
P2—C211 | 1.828 (2) | C212—C213 | 1.386 (3) |
P2—C221 | 1.830 (2) | C213—C214 | 1.364 (4) |
P2—C231 | 1.815 (3) | C214—C215 | 1.365 (4) |
C111—C112 | 1.393 (3) | C215—C216 | 1.386 (4) |
C111—C116 | 1.392 (3) | C221—C222 | 1.373 (3) |
C112—C113 | 1.384 (4) | C221—C226 | 1.388 (3) |
C113—C114 | 1.370 (4) | C222—C223 | 1.385 (3) |
C114—C115 | 1.383 (4) | C223—C224 | 1.357 (4) |
C115—C116 | 1.368 (4) | C224—C225 | 1.374 (4) |
C121—C122 | 1.374 (4) | C225—C226 | 1.387 (4) |
C121—C126 | 1.377 (3) | C231—C232 | 1.380 (4) |
C122—C123 | 1.379 (4) | C231—C236 | 1.395 (4) |
C123—C124 | 1.361 (4) | C232—C233 | 1.380 (4) |
C124—C125 | 1.368 (4) | C233—C234 | 1.360 (4) |
C125—C126 | 1.377 (4) | C234—C235 | 1.359 (4) |
C131—C132 | 1.386 (3) | C235—C236 | 1.385 (4) |
C1—Pd—P1 | 91.50 (7) | C125—C126—C121 | 121.0 (3) |
C1—Pd—P2 | 90.63 (7) | C136—C131—C132 | 118.6 (2) |
P1—Pd—P2 | 177.38 (2) | C132—C131—P1 | 118.4 (2) |
C1—Pd—Cl | 175.23 (8) | C136—C131—P1 | 123.0 (2) |
P1—Pd—Cl | 88.97 (2) | C133—C132—C131 | 121.1 (3) |
P2—Pd—Cl | 89.03 (2) | C134—C133—C132 | 119.6 (3) |
C111—P1—C121 | 105.56 (11) | C135—C134—C133 | 119.9 (3) |
C111—P1—C131 | 101.16 (11) | C134—C135—C136 | 120.6 (3) |
C121—P1—C131 | 104.27 (11) | C131—C136—C135 | 120.2 (3) |
C111—P1—Pd | 115.52 (8) | C216—C211—C212 | 118.4 (2) |
C121—P1—Pd | 109.92 (9) | C212—C211—P2 | 119.42 (19) |
C131—P1—Pd | 119.01 (8) | C216—C211—P2 | 122.2 (2) |
C211—P2—C221 | 103.27 (11) | C213—C212—C211 | 120.5 (2) |
C211—P2—C231 | 107.09 (12) | C214—C213—C212 | 120.1 (3) |
C221—P2—C231 | 100.86 (11) | C213—C214—C215 | 120.4 (3) |
C211—P2—Pd | 113.09 (8) | C214—C215—C216 | 120.7 (3) |
C221—P2—Pd | 120.36 (8) | C215—C216—C211 | 119.9 (3) |
C231—P2—Pd | 110.81 (8) | C222—C221—C226 | 117.4 (2) |
C116—C111—C112 | 117.9 (2) | C222—C221—P2 | 122.00 (19) |
C112—C111—P1 | 120.9 (2) | C226—C221—P2 | 120.5 (2) |
C116—C111—P1 | 121.2 (2) | C221—C222—C223 | 121.6 (3) |
C113—C112—C111 | 120.7 (3) | C224—C223—C222 | 120.2 (3) |
C114—C113—C112 | 120.1 (3) | C223—C224—C225 | 119.8 (3) |
C113—C114—C115 | 120.2 (3) | C224—C225—C226 | 119.8 (3) |
C116—C115—C114 | 119.7 (3) | C225—C226—C221 | 121.1 (3) |
C115—C116—C111 | 121.5 (3) | C232—C231—C236 | 117.8 (3) |
C122—C121—C126 | 117.7 (2) | C232—C231—P2 | 123.8 (2) |
C122—C121—P1 | 119.5 (2) | C236—C231—P2 | 118.0 (2) |
C126—C121—P1 | 122.7 (2) | C231—C232—C233 | 120.5 (3) |
C121—C122—C123 | 121.5 (3) | C234—C233—C232 | 120.9 (3) |
C124—C123—C122 | 120.0 (3) | C235—C234—C233 | 119.9 (3) |
C123—C124—C125 | 119.6 (3) | C234—C235—C236 | 120.1 (3) |
C124—C125—C126 | 120.3 (3) | C235—C236—C231 | 120.7 (3) |
Cl—Pd—P1—C111 | 65.25 (9) | Cl—Pd—P2—C211 | −70.73 (9) |
Cl—Pd—P1—C121 | −54.03 (8) | Cl—Pd—P2—C221 | 166.67 (10) |
Cl—Pd—P1—C131 | −174.08 (10) | Cl—Pd—P2—C231 | 49.52 (9) |
Experimental details
Crystal data | |
Chemical formula | [PdCl(CH3)(C18H15P)2] |
Mr | 681.42 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 11.8068 (4), 23.3389 (9), 12.3650 (5) |
β (°) | 111.537 (1) |
V (Å3) | 3169.4 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.80 |
Crystal size (mm) | 0.37 × 0.24 × 0.11 |
Data collection | |
Diffractometer | Siemens SMART CCD diffractometer |
Absorption correction | Empirical (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.621, 0.735 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32413, 9837, 4925 |
Rint | 0.076 |
(sin θ/λ)max (Å−1) | 0.739 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.071, 0.85 |
No. of reflections | 9837 |
No. of parameters | 372 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.61 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg 1997), SHELXL97.
Pd—P1 | 2.3289 (7) | P1—C121 | 1.825 (3) |
Pd—P2 | 2.3224 (7) | P1—C131 | 1.835 (2) |
Pd—Cl | 2.4227 (6) | P2—C211 | 1.828 (2) |
Pd—C1 | 2.054 (2) | P2—C221 | 1.830 (2) |
P1—C111 | 1.827 (3) | P2—C231 | 1.815 (3) |
C1—Pd—P1 | 91.50 (7) | C111—P1—Pd | 115.52 (8) |
C1—Pd—P2 | 90.63 (7) | C121—P1—Pd | 109.92 (9) |
P1—Pd—P2 | 177.38 (2) | C131—P1—Pd | 119.01 (8) |
C1—Pd—Cl | 175.23 (8) | C211—P2—C221 | 103.27 (11) |
P1—Pd—Cl | 88.97 (2) | C211—P2—C231 | 107.09 (12) |
P2—Pd—Cl | 89.03 (2) | C221—P2—C231 | 100.86 (11) |
C111—P1—C121 | 105.56 (11) | C211—P2—Pd | 113.09 (8) |
C111—P1—C131 | 101.16 (11) | C221—P2—Pd | 120.36 (8) |
C121—P1—C131 | 104.27 (11) | C231—P2—Pd | 110.81 (8) |
Cl—Pd—P1—C111 | 65.25 (9) | Cl—Pd—P2—C211 | −70.73 (9) |
Cl—Pd—P1—C121 | −54.03 (8) | Cl—Pd—P2—C221 | 166.67 (10) |
Cl—Pd—P1—C131 | −174.08 (10) | Cl—Pd—P2—C231 | 49.52 (9) |
Complex | M—L (Å) | M—C (Å) | M—Cl (Å) | Typea | Refs |
[PdMeCl(PPh3)2] | 2.3289 (7) | 2.054 (2) | 2.4227 (6) | I | (i) |
2.3224 (7) | |||||
[PdMeCl(AsPh3)2] | 2.3989 (5) | 2.095 (4) | 2.4086 (11) | I | (ii) |
2.4067 (5) | |||||
[PtMeCl(PPh3)2] | 2.295 (3) | 2.08 (1) | 2.431 (3) | I | (iii) |
2.298 (3) | |||||
[PtMeCl(PPh3)2] | 2.2955 (10) | 2.02 (2) | 2.415 (5) | II | (iv) |
[PtMeCl(AsPh3)2] | 2.3856 (9) | 2.073 (8) | 2.410 (2) | I | (v) |
2.3786 (9) | |||||
[PdMeCl(PPh2Fc)2] | 2.3328 (10) | 2.108 (10) | 2.378 (3) | (vi) | |
[PdCH2ClCl(PPh3)2] | 2.337 (1) | 2.031 (2) | 2.402 (1) | (vii) | |
2.329 (1) | |||||
[PdPhCl(PPh3)2] | 2.316 (1) | 2.016 (3) | 2.407 (1) | (viii) | |
2.324 (1) | |||||
[Pd(Cl)2(PPh3)2] | 2.337 (1) | 2.290 (1) | II | (ix) | |
[Pt(Cl)2(PPh3)2] | 2.3175 (12) | 2.2997 (11) | II | (x) |
Notes: (a) See Comment section for definition of structure types. References: (i) this work; (ii) Rath et al. (1995); (iii) Bardi & Piazzesi (1981); (iv) Otto et al. (1995); (v) Roodt et al. (1995); (vi) Otto et al. (2000); (vii) McCrindle et al. (1995); (viii) Flemming et al. (1998); (ix) Ferguson et al. (1982); (x) Johansson & Otto (2000). |
As part of a systematic investigation of the structure–reactivity relationships for the platinum group metal complexes, crystals of trans-chloro(methyl)bis(tripenylphosphine)palladium(II), (I), were prepared. The complex was found to be isomorphous with the platinum analogue (Bardi & Piazzesi, 1981), as well as with the closely related palladium and platinum triphenylarsine complexes (Rath et al., 1995; Roodt et al., 1995).
The Pd atom has a slightly distorted square-planar coordination environment with the phosphine ligands in a trans orientation. The P1—Pd—P2 angle is 177.38 (2)°, with Pd—P1 and Pd—P2 bond distances of 2.3289 (7) and 2.3224 (7) Å, respectively (see Table 1). The Pd—Cl bond is relatively long at 2.4227 (6) Å, obviously due to a strong labilizing influence of a trans-Me ligand [Pd—C1 2.054 (2) Å]. The C1—Pd—Cl angle of 175.23 (8)° deviates substantially from 180°. The slight distortion of the Pd square-planar coordination is also manifested in some decrease of the P1—Pd—Cl and P2—Pd—Cl [88.97 (2) and 89.03 (2)°, respectively] and a corresponding increase of the C1—Pd—P1 and C1—Pd—P2 angles [91.50 (7) and 90.63 (7)°, respectively].
All bond distances and angles within the PPh3 ligands are within normal ranges (see Table 1). The PPh3 groups are in almost perfectly eclipsed conformation with the biggest pseudo-torsion angle of the CPh—P1···P2—CPh type being equal to only 7.5°.
In Table 2, the title compound is compared with other closely related PtII and PdII complexes from the literature. It is noteworthy that all complexes with the general formula [MRY(EPh3)2], where M = Pd or Pt, RY = Cl2 or MeCl, and E = P or As, belong to one of just two types of isomorphous structures. The non-symmetric complexes with RY = MeCl are isomorphous with the title compound (P21/n, Z = 4, type I), whereas the complexes with symmetric substitution (RY = Cl2) crystallize in the triclinic system, the molecule of the complex occupying a special position in the inversion centre (P1, Z = 1, type II). The triclinic modification of complex [PtMeCl(PPh3)2] (Otto et al., 1995) presents a notable exception from this rule: this structure accommodates a non-symmetric molecule within the type II crystal structure, the Me group and Cl atoms being disordered over two positions related by the inversion centre.
Another observation, which follows from the data presented in Table 2, is that the Pt—L bonds are slightly shorter than the Pd—L bonds in corresponding complexes with differences of ca 0.030 and 0.020 Å for L = P and As, respectively. This observation could, to some extent, be explained by the difference in the covalent radii of Pd (1.380 Å) and Pt (1.370 Å) (Sheldrick, 1997b). The M—Cl bonds are very similar though, while no conclusive deductions could be made concerning the M—C bond distance due to the large uncertainty associated with them.