Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270111033051/fg3223sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270111033051/fg3223Isup2.hkl |
CCDC reference: 846630
The complex trans-[PdCl2(PPh3)2] was dissolved in warm ethanol by vigorous shaking. The newly prepared solution was left standing for 1 week at room temperature. After solvent evaporation, yellow prismatic crystals were formed on the bottom of the glass crystallizer. A well shaped clear crystal was selected for the single-crystal X-ray diffraction experiment.
Non-hydrogen atoms were refined anisotropically and the H atoms were placed at their calculated positions using a riding model, with Uiso(H) = 1.2Ueq(C).
Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006); software used to prepare material for publication: WinGX (Farrugia, 1999).
[PdCl2(C18H15P)2] | Z = 2 |
Mr = 701.84 | F(000) = 712 |
Triclinic, P1 | Dx = 1.474 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.9830 (3) Å | Cell parameters from 14503 reflections |
b = 11.3023 (3) Å | θ = 2.9–27.5° |
c = 15.6037 (5) Å | µ = 0.88 mm−1 |
α = 89.947 (2)° | T = 294 K |
β = 89.539 (1)° | Prism, orange |
γ = 63.926 (1)° | 0.12 × 0.09 × 0.04 mm |
V = 1581.34 (8) Å3 |
Nonius KappaCCD diffractometer | 7114 independent reflections |
Radiation source: Enraf–Nonius FR590 | 4370 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.073 |
Detector resolution: 9 pixels mm-1 | θmax = 27.5°, θmin = 3.3° |
CCD rotation images, thick slices scans | h = −12→12 |
Absorption correction: gaussian (Coppens et al., 1965) | k = −14→14 |
Tmin = 0.891, Tmax = 0.962 | l = −19→20 |
27320 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) = 0.128 | H-atom parameters constrained |
S = 1.01 | w = 1/[σ2(Fo2) + (0.0644P)2] where P = (Fo2 + 2Fc2)/3 |
7114 reflections | (Δ/σ)max < 0.001 |
373 parameters | Δρmax = 0.92 e Å−3 |
0 restraints | Δρmin = −0.92 e Å−3 |
[PdCl2(C18H15P)2] | γ = 63.926 (1)° |
Mr = 701.84 | V = 1581.34 (8) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.9830 (3) Å | Mo Kα radiation |
b = 11.3023 (3) Å | µ = 0.88 mm−1 |
c = 15.6037 (5) Å | T = 294 K |
α = 89.947 (2)° | 0.12 × 0.09 × 0.04 mm |
β = 89.539 (1)° |
Nonius KappaCCD diffractometer | 7114 independent reflections |
Absorption correction: gaussian (Coppens et al., 1965) | 4370 reflections with I > 2σ(I) |
Tmin = 0.891, Tmax = 0.962 | Rint = 0.073 |
27320 measured reflections |
R[F2 > 2σ(F2)] = 0.046 | 0 restraints |
wR(F2) = 0.128 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.92 e Å−3 |
7114 reflections | Δρmin = −0.92 e Å−3 |
373 parameters |
Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 | 0.5 | 0.5 | 0.03699 (13) | |
Pd2 | 1 | 0 | 0 | 0.03937 (14) | |
P2 | 0.79269 (11) | 0.20663 (10) | 0.01572 (7) | 0.0398 (3) | |
Cl1 | 0.15336 (13) | 0.46347 (10) | 0.38230 (7) | 0.0533 (3) | |
P1 | 0.03696 (12) | 0.28211 (10) | 0.50286 (7) | 0.0375 (2) | |
Cl2 | 1.14525 (12) | 0.10835 (10) | −0.02149 (8) | 0.0577 (3) | |
C121 | 0.1617 (5) | 0.1683 (4) | 0.4229 (3) | 0.0410 (9) | |
C212 | 0.8272 (5) | 0.2546 (4) | −0.1545 (3) | 0.0561 (12) | |
H212 | 0.9281 | 0.2183 | −0.1412 | 0.067* | |
C221 | 0.8403 (4) | 0.3298 (4) | 0.0632 (3) | 0.0442 (10) | |
C112 | 0.1540 (5) | 0.2493 (4) | 0.6680 (3) | 0.0502 (11) | |
H112 | 0.1406 | 0.3358 | 0.6634 | 0.06* | |
C226 | 0.9207 (5) | 0.2987 (5) | 0.1390 (3) | 0.0581 (12) | |
H226 | 0.948 | 0.2166 | 0.1639 | 0.07* | |
C231 | 0.6302 (4) | 0.2204 (4) | 0.0766 (3) | 0.0419 (9) | |
C211 | 0.7242 (5) | 0.2653 (4) | −0.0912 (3) | 0.0449 (10) | |
C113 | 0.2170 (5) | 0.1779 (5) | 0.7414 (3) | 0.0604 (13) | |
H113 | 0.2474 | 0.2162 | 0.7851 | 0.072* | |
C236 | 0.5472 (5) | 0.1551 (4) | 0.0504 (3) | 0.0537 (11) | |
H236 | 0.5758 | 0.1027 | 0.0014 | 0.064* | |
C222 | 0.8013 (5) | 0.4527 (4) | 0.0264 (3) | 0.0554 (12) | |
H222 | 0.7457 | 0.4762 | −0.0236 | 0.066* | |
C114 | 0.2346 (5) | 0.0505 (5) | 0.7498 (3) | 0.0624 (13) | |
H114 | 0.2726 | 0.0042 | 0.8001 | 0.075* | |
C111 | 0.1110 (4) | 0.1929 (4) | 0.6016 (3) | 0.0402 (9) | |
C213 | 0.7819 (6) | 0.2972 (5) | −0.2370 (3) | 0.0683 (14) | |
H213 | 0.8515 | 0.2931 | −0.2783 | 0.082* | |
C232 | 0.5824 (5) | 0.2986 (4) | 0.1506 (3) | 0.0566 (12) | |
H232 | 0.6346 | 0.3442 | 0.1698 | 0.068* | |
C234 | 0.3788 (5) | 0.2438 (5) | 0.1681 (4) | 0.0698 (15) | |
H234 | 0.2946 | 0.2516 | 0.1984 | 0.084* | |
C134 | −0.4287 (6) | 0.3179 (5) | 0.4456 (4) | 0.0743 (16) | |
H134 | −0.5247 | 0.3291 | 0.4335 | 0.089* | |
C115 | 0.1960 (5) | −0.0075 (4) | 0.6836 (3) | 0.0580 (12) | |
H115 | 0.2107 | −0.0944 | 0.6885 | 0.07* | |
C215 | 0.5311 (6) | 0.3580 (5) | −0.1960 (3) | 0.0738 (16) | |
H215 | 0.4308 | 0.3923 | −0.2104 | 0.089* | |
C136 | −0.2106 (5) | 0.2259 (4) | 0.5327 (3) | 0.0502 (11) | |
H136 | −0.1595 | 0.1735 | 0.5787 | 0.06* | |
C123 | 0.4137 (6) | 0.0452 (5) | 0.3726 (4) | 0.0762 (16) | |
H123 | 0.515 | 0.0212 | 0.3784 | 0.091* | |
C223 | 0.8466 (6) | 0.5409 (5) | 0.0653 (4) | 0.0737 (16) | |
H223 | 0.8239 | 0.622 | 0.0401 | 0.088* | |
C132 | −0.2229 (5) | 0.3637 (4) | 0.4133 (3) | 0.0607 (13) | |
H132 | −0.1796 | 0.405 | 0.379 | 0.073* | |
C124 | 0.3648 (7) | −0.0049 (5) | 0.3065 (4) | 0.0739 (15) | |
H124 | 0.4329 | −0.0634 | 0.2677 | 0.089* | |
C131 | −0.1442 (4) | 0.2882 (4) | 0.4830 (3) | 0.0401 (9) | |
C135 | −0.3536 (6) | 0.2422 (5) | 0.5135 (4) | 0.0683 (14) | |
H135 | −0.3983 | 0.2013 | 0.5472 | 0.082* | |
C225 | 0.9603 (5) | 0.3879 (5) | 0.1777 (4) | 0.0703 (15) | |
H225 | 1.0117 | 0.3671 | 0.2292 | 0.084* | |
C216 | 0.5736 (5) | 0.3205 (4) | −0.1130 (3) | 0.0585 (12) | |
H216 | 0.5019 | 0.3318 | −0.0712 | 0.07* | |
C122 | 0.3136 (5) | 0.1309 (4) | 0.4304 (3) | 0.0586 (12) | |
H122 | 0.3479 | 0.1644 | 0.4751 | 0.07* | |
C224 | 0.9236 (6) | 0.5078 (6) | 0.1399 (4) | 0.0779 (17) | |
H224 | 0.9519 | 0.5673 | 0.1658 | 0.094* | |
C126 | 0.1133 (5) | 0.1181 (4) | 0.3561 (3) | 0.0528 (11) | |
H126 | 0.0121 | 0.142 | 0.3499 | 0.063* | |
C125 | 0.2164 (7) | 0.0309 (5) | 0.2977 (3) | 0.0703 (15) | |
H125 | 0.1834 | −0.0028 | 0.2525 | 0.084* | |
C214 | 0.6342 (6) | 0.3456 (5) | −0.2575 (3) | 0.0738 (16) | |
H214 | 0.604 | 0.3702 | −0.3136 | 0.089* | |
C133 | −0.3629 (6) | 0.3776 (5) | 0.3950 (4) | 0.0764 (17) | |
H133 | −0.4138 | 0.4276 | 0.3482 | 0.092* | |
C235 | 0.4235 (5) | 0.1672 (5) | 0.0960 (4) | 0.0653 (14) | |
H235 | 0.3696 | 0.1227 | 0.0776 | 0.078* | |
C233 | 0.4575 (6) | 0.3083 (5) | 0.1953 (4) | 0.0733 (15) | |
H233 | 0.4272 | 0.3598 | 0.2447 | 0.088* | |
C116 | 0.1356 (5) | 0.0617 (4) | 0.6100 (3) | 0.0493 (11) | |
H116 | 0.1108 | 0.0209 | 0.5653 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.0399 (2) | 0.0330 (2) | 0.0400 (3) | −0.01772 (19) | 0.00110 (19) | 0.00115 (18) |
Pd2 | 0.0376 (2) | 0.0363 (2) | 0.0421 (3) | −0.01432 (19) | −0.00205 (19) | −0.00206 (18) |
P2 | 0.0387 (6) | 0.0353 (5) | 0.0427 (6) | −0.0136 (5) | −0.0013 (5) | −0.0023 (4) |
Cl1 | 0.0589 (7) | 0.0469 (6) | 0.0531 (7) | −0.0227 (5) | 0.0149 (5) | 0.0006 (5) |
P1 | 0.0423 (6) | 0.0334 (5) | 0.0391 (6) | −0.0188 (4) | −0.0006 (5) | 0.0006 (4) |
Cl2 | 0.0463 (6) | 0.0473 (6) | 0.0822 (9) | −0.0231 (5) | 0.0043 (6) | −0.0053 (6) |
C121 | 0.049 (2) | 0.034 (2) | 0.042 (2) | −0.0204 (18) | 0.0053 (19) | −0.0007 (17) |
C212 | 0.047 (3) | 0.062 (3) | 0.054 (3) | −0.019 (2) | 0.005 (2) | 0.002 (2) |
C221 | 0.040 (2) | 0.043 (2) | 0.050 (3) | −0.0191 (19) | 0.0079 (19) | −0.0073 (19) |
C112 | 0.050 (3) | 0.040 (2) | 0.053 (3) | −0.0123 (19) | −0.005 (2) | −0.005 (2) |
C226 | 0.056 (3) | 0.062 (3) | 0.055 (3) | −0.024 (2) | −0.007 (2) | −0.007 (2) |
C231 | 0.041 (2) | 0.037 (2) | 0.045 (2) | −0.0154 (18) | −0.0044 (19) | 0.0014 (18) |
C211 | 0.046 (2) | 0.035 (2) | 0.045 (3) | −0.0101 (18) | −0.001 (2) | −0.0020 (18) |
C113 | 0.057 (3) | 0.063 (3) | 0.042 (3) | −0.008 (2) | −0.012 (2) | −0.008 (2) |
C236 | 0.043 (2) | 0.052 (3) | 0.066 (3) | −0.020 (2) | −0.007 (2) | −0.003 (2) |
C222 | 0.054 (3) | 0.044 (2) | 0.067 (3) | −0.020 (2) | 0.008 (2) | −0.008 (2) |
C114 | 0.057 (3) | 0.063 (3) | 0.049 (3) | −0.010 (2) | −0.005 (2) | 0.010 (2) |
C111 | 0.037 (2) | 0.036 (2) | 0.042 (2) | −0.0099 (17) | −0.0007 (18) | 0.0018 (17) |
C213 | 0.075 (4) | 0.068 (3) | 0.046 (3) | −0.017 (3) | 0.006 (3) | 0.008 (2) |
C232 | 0.056 (3) | 0.062 (3) | 0.059 (3) | −0.034 (2) | 0.011 (2) | −0.013 (2) |
C234 | 0.046 (3) | 0.072 (3) | 0.091 (4) | −0.026 (3) | 0.008 (3) | 0.013 (3) |
C134 | 0.042 (3) | 0.072 (4) | 0.104 (5) | −0.020 (3) | −0.012 (3) | −0.010 (3) |
C115 | 0.063 (3) | 0.046 (3) | 0.060 (3) | −0.020 (2) | −0.007 (2) | 0.014 (2) |
C215 | 0.062 (3) | 0.073 (3) | 0.062 (4) | −0.007 (3) | −0.015 (3) | 0.015 (3) |
C136 | 0.048 (3) | 0.056 (3) | 0.052 (3) | −0.027 (2) | 0.000 (2) | −0.001 (2) |
C123 | 0.057 (3) | 0.080 (4) | 0.082 (4) | −0.021 (3) | 0.018 (3) | 0.000 (3) |
C223 | 0.072 (4) | 0.046 (3) | 0.106 (5) | −0.029 (3) | 0.022 (3) | −0.019 (3) |
C132 | 0.060 (3) | 0.056 (3) | 0.070 (3) | −0.029 (2) | −0.017 (3) | 0.015 (2) |
C124 | 0.081 (4) | 0.061 (3) | 0.070 (4) | −0.023 (3) | 0.029 (3) | −0.011 (3) |
C131 | 0.042 (2) | 0.036 (2) | 0.044 (2) | −0.0179 (18) | −0.0034 (18) | 0.0000 (17) |
C135 | 0.057 (3) | 0.086 (4) | 0.076 (4) | −0.045 (3) | 0.006 (3) | −0.005 (3) |
C225 | 0.051 (3) | 0.082 (4) | 0.078 (4) | −0.030 (3) | 0.003 (3) | −0.030 (3) |
C216 | 0.047 (3) | 0.061 (3) | 0.051 (3) | −0.009 (2) | −0.001 (2) | 0.005 (2) |
C122 | 0.050 (3) | 0.064 (3) | 0.060 (3) | −0.024 (2) | 0.009 (2) | −0.005 (2) |
C224 | 0.066 (3) | 0.080 (4) | 0.099 (5) | −0.042 (3) | 0.021 (3) | −0.047 (4) |
C126 | 0.059 (3) | 0.046 (3) | 0.052 (3) | −0.021 (2) | 0.007 (2) | −0.006 (2) |
C125 | 0.097 (4) | 0.061 (3) | 0.055 (3) | −0.036 (3) | 0.005 (3) | −0.011 (2) |
C214 | 0.083 (4) | 0.063 (3) | 0.047 (3) | −0.005 (3) | −0.008 (3) | 0.012 (2) |
C133 | 0.067 (3) | 0.063 (3) | 0.096 (5) | −0.025 (3) | −0.036 (3) | 0.021 (3) |
C235 | 0.043 (3) | 0.062 (3) | 0.095 (4) | −0.027 (2) | −0.005 (3) | 0.001 (3) |
C233 | 0.064 (3) | 0.086 (4) | 0.070 (4) | −0.034 (3) | 0.024 (3) | −0.016 (3) |
C116 | 0.056 (3) | 0.040 (2) | 0.051 (3) | −0.020 (2) | −0.009 (2) | 0.0063 (19) |
Pd1—Cl1 | 2.2996 (11) | C232—C233 | 1.385 (6) |
Pd1—Cl1i | 2.2996 (11) | C232—H232 | 0.93 |
Pd1—P1 | 2.3247 (10) | C234—C233 | 1.357 (7) |
Pd1—P1i | 2.3247 (10) | C234—C235 | 1.366 (7) |
Pd2—Cl2 | 2.2950 (11) | C234—H234 | 0.93 |
Pd2—Cl2ii | 2.2950 (11) | C134—C135 | 1.365 (7) |
Pd2—P2ii | 2.3540 (10) | C134—C133 | 1.375 (8) |
Pd2—P2 | 2.3540 (10) | C134—H134 | 0.93 |
P2—C221 | 1.817 (4) | C115—C116 | 1.375 (6) |
P2—C211 | 1.818 (4) | C115—H115 | 0.93 |
P2—C231 | 1.819 (4) | C215—C214 | 1.362 (8) |
P1—C131 | 1.809 (4) | C215—C216 | 1.374 (6) |
P1—C111 | 1.815 (4) | C215—H215 | 0.93 |
P1—C121 | 1.825 (4) | C136—C131 | 1.391 (6) |
C121—C126 | 1.376 (6) | C136—C135 | 1.392 (6) |
C121—C122 | 1.390 (6) | C136—H136 | 0.93 |
C212—C213 | 1.382 (6) | C123—C124 | 1.371 (8) |
C212—C211 | 1.386 (6) | C123—C122 | 1.373 (7) |
C212—H212 | 0.93 | C123—H123 | 0.93 |
C221—C226 | 1.390 (6) | C223—C224 | 1.359 (8) |
C221—C222 | 1.392 (6) | C223—H223 | 0.93 |
C112—C111 | 1.383 (5) | C132—C133 | 1.369 (7) |
C112—C113 | 1.386 (6) | C132—C131 | 1.397 (6) |
C112—H112 | 0.93 | C132—H132 | 0.93 |
C226—C225 | 1.376 (6) | C124—C125 | 1.361 (8) |
C226—H226 | 0.93 | C124—H124 | 0.93 |
C231—C236 | 1.394 (6) | C135—H135 | 0.93 |
C231—C232 | 1.402 (6) | C225—C224 | 1.372 (8) |
C211—C216 | 1.396 (6) | C225—H225 | 0.93 |
C113—C114 | 1.378 (7) | C216—H216 | 0.93 |
C113—H113 | 0.93 | C122—H122 | 0.93 |
C236—C235 | 1.374 (7) | C224—H224 | 0.93 |
C236—H236 | 0.93 | C126—C125 | 1.400 (7) |
C222—C223 | 1.403 (6) | C126—H126 | 0.93 |
C222—H222 | 0.93 | C125—H125 | 0.93 |
C114—C115 | 1.370 (6) | C214—H214 | 0.93 |
C114—H114 | 0.93 | C133—H133 | 0.93 |
C111—C116 | 1.399 (5) | C235—H235 | 0.93 |
C213—C214 | 1.370 (7) | C233—H233 | 0.93 |
C213—H213 | 0.93 | C116—H116 | 0.93 |
Cl1—Pd1—Cl1i | 180 | C233—C234—C235 | 119.8 (5) |
Cl1—Pd1—P1 | 92.41 (4) | C233—C234—H234 | 120.1 |
Cl1i—Pd1—P1 | 87.59 (4) | C235—C234—H234 | 120.1 |
Cl1—Pd1—P1i | 87.59 (4) | C135—C134—C133 | 120.2 (5) |
Cl1i—Pd1—P1i | 92.41 (4) | C135—C134—H134 | 119.9 |
P1—Pd1—P1i | 180 | C133—C134—H134 | 119.9 |
Cl2—Pd2—Cl2ii | 180 | C114—C115—C116 | 120.5 (4) |
Cl2—Pd2—P2ii | 91.69 (4) | C114—C115—H115 | 119.8 |
Cl2ii—Pd2—P2ii | 88.31 (4) | C116—C115—H115 | 119.8 |
Cl2—Pd2—P2 | 88.31 (4) | C214—C215—C216 | 120.7 (5) |
Cl2ii—Pd2—P2 | 91.69 (4) | C214—C215—H215 | 119.6 |
P2ii—Pd2—P2 | 180 | C216—C215—H215 | 119.6 |
C221—P2—C211 | 106.3 (2) | C131—C136—C135 | 119.9 (4) |
C221—P2—C231 | 104.29 (19) | C131—C136—H136 | 120 |
C211—P2—C231 | 105.32 (19) | C135—C136—H136 | 120 |
C221—P2—Pd2 | 112.85 (14) | C124—C123—C122 | 120.2 (5) |
C211—P2—Pd2 | 107.30 (13) | C124—C123—H123 | 119.9 |
C231—P2—Pd2 | 119.82 (13) | C122—C123—H123 | 119.9 |
C131—P1—C111 | 109.25 (19) | C224—C223—C222 | 120.0 (5) |
C131—P1—C121 | 105.45 (19) | C224—C223—H223 | 120 |
C111—P1—C121 | 101.61 (18) | C222—C223—H223 | 120 |
C131—P1—Pd1 | 105.42 (12) | C133—C132—C131 | 120.7 (5) |
C111—P1—Pd1 | 116.18 (13) | C133—C132—H132 | 119.6 |
C121—P1—Pd1 | 118.35 (13) | C131—C132—H132 | 119.6 |
C126—C121—C122 | 118.6 (4) | C125—C124—C123 | 119.9 (5) |
C126—C121—P1 | 123.6 (3) | C125—C124—H124 | 120 |
C122—C121—P1 | 117.8 (3) | C123—C124—H124 | 120 |
C213—C212—C211 | 120.9 (5) | C136—C131—C132 | 118.5 (4) |
C213—C212—H212 | 119.6 | C136—C131—P1 | 124.9 (3) |
C211—C212—H212 | 119.6 | C132—C131—P1 | 116.6 (3) |
C226—C221—C222 | 118.9 (4) | C134—C135—C136 | 120.4 (5) |
C226—C221—P2 | 118.2 (3) | C134—C135—H135 | 119.8 |
C222—C221—P2 | 122.8 (3) | C136—C135—H135 | 119.8 |
C111—C112—C113 | 120.6 (4) | C224—C225—C226 | 119.7 (5) |
C111—C112—H112 | 119.7 | C224—C225—H225 | 120.1 |
C113—C112—H112 | 119.7 | C226—C225—H225 | 120.1 |
C225—C226—C221 | 120.8 (5) | C215—C216—C211 | 120.1 (5) |
C225—C226—H226 | 119.6 | C215—C216—H216 | 119.9 |
C221—C226—H226 | 119.6 | C211—C216—H216 | 119.9 |
C236—C231—C232 | 117.5 (4) | C123—C122—C121 | 120.9 (5) |
C236—C231—P2 | 121.1 (3) | C123—C122—H122 | 119.6 |
C232—C231—P2 | 121.4 (3) | C121—C122—H122 | 119.6 |
C212—C211—C216 | 118.2 (4) | C223—C224—C225 | 121.0 (5) |
C212—C211—P2 | 118.2 (3) | C223—C224—H224 | 119.5 |
C216—C211—P2 | 123.6 (4) | C225—C224—H224 | 119.5 |
C114—C113—C112 | 120.3 (4) | C121—C126—C125 | 120.0 (5) |
C114—C113—H113 | 119.9 | C121—C126—H126 | 120 |
C112—C113—H113 | 119.9 | C125—C126—H126 | 120 |
C235—C236—C231 | 120.8 (5) | C124—C125—C126 | 120.4 (5) |
C235—C236—H236 | 119.6 | C124—C125—H125 | 119.8 |
C231—C236—H236 | 119.6 | C126—C125—H125 | 119.8 |
C221—C222—C223 | 119.5 (5) | C215—C214—C213 | 120.3 (5) |
C221—C222—H222 | 120.3 | C215—C214—H214 | 119.8 |
C223—C222—H222 | 120.3 | C213—C214—H214 | 119.8 |
C115—C114—C113 | 119.7 (4) | C132—C133—C134 | 120.3 (5) |
C115—C114—H114 | 120.2 | C132—C133—H133 | 119.9 |
C113—C114—H114 | 120.2 | C134—C133—H133 | 119.9 |
C112—C111—C116 | 118.1 (4) | C234—C235—C236 | 120.8 (5) |
C112—C111—P1 | 121.2 (3) | C234—C235—H235 | 119.6 |
C116—C111—P1 | 120.5 (3) | C236—C235—H235 | 119.6 |
C214—C213—C212 | 119.6 (5) | C234—C233—C232 | 120.9 (5) |
C214—C213—H213 | 120.2 | C234—C233—H233 | 119.6 |
C212—C213—H213 | 120.2 | C232—C233—H233 | 119.6 |
C233—C232—C231 | 120.2 (4) | C115—C116—C111 | 120.8 (4) |
C233—C232—H232 | 119.9 | C115—C116—H116 | 119.6 |
C231—C232—H232 | 119.9 | C111—C116—H116 | 119.6 |
C131—P1—C121—C126 | 8.5 (4) | C211—C212—C213—C214 | −2.7 (8) |
C111—P1—C121—C126 | 122.5 (4) | C236—C231—C232—C233 | 0.5 (7) |
Pd1—P1—C121—C126 | −109.0 (3) | P2—C231—C232—C233 | 179.4 (4) |
C131—P1—C121—C122 | −171.5 (3) | C113—C114—C115—C116 | −2.0 (8) |
C111—P1—C121—C122 | −57.5 (4) | C221—C222—C223—C224 | −2.2 (7) |
Pd1—P1—C121—C122 | 71.0 (4) | C122—C123—C124—C125 | 0.4 (9) |
C211—P2—C221—C226 | −168.6 (3) | C135—C136—C131—C132 | −1.4 (7) |
C231—P2—C221—C226 | 80.4 (4) | C135—C136—C131—P1 | 177.2 (4) |
Pd2—P2—C221—C226 | −51.2 (4) | C133—C132—C131—C136 | 0.9 (7) |
C211—P2—C221—C222 | 10.7 (4) | C133—C132—C131—P1 | −177.9 (4) |
C231—P2—C221—C222 | −100.3 (4) | C111—P1—C131—C136 | −4.2 (4) |
Pd2—P2—C221—C222 | 128.1 (3) | C121—P1—C131—C136 | 104.3 (4) |
C222—C221—C226—C225 | 0.5 (7) | Pd1—P1—C131—C136 | −129.7 (3) |
P2—C221—C226—C225 | 179.8 (4) | C111—P1—C131—C132 | 174.4 (3) |
C221—P2—C231—C236 | 170.1 (3) | C121—P1—C131—C132 | −77.0 (4) |
C211—P2—C231—C236 | 58.3 (4) | Pd1—P1—C131—C132 | 48.9 (4) |
Pd2—P2—C231—C236 | −62.5 (4) | C133—C134—C135—C136 | 0.7 (9) |
C221—P2—C231—C232 | −8.8 (4) | C131—C136—C135—C134 | 0.7 (8) |
C211—P2—C231—C232 | −120.6 (4) | C221—C226—C225—C224 | −1.7 (7) |
Pd2—P2—C231—C232 | 118.6 (3) | C214—C215—C216—C211 | −1.9 (8) |
C213—C212—C211—C216 | −0.1 (7) | C212—C211—C216—C215 | 2.4 (7) |
C213—C212—C211—P2 | 179.9 (4) | P2—C211—C216—C215 | −177.6 (4) |
C221—P2—C211—C212 | 75.6 (4) | C124—C123—C122—C121 | −0.1 (8) |
C231—P2—C211—C212 | −174.1 (3) | C126—C121—C122—C123 | −0.2 (7) |
Pd2—P2—C211—C212 | −45.4 (4) | P1—C121—C122—C123 | 179.8 (4) |
C221—P2—C211—C216 | −104.4 (4) | C222—C223—C224—C225 | 1.0 (8) |
C231—P2—C211—C216 | 5.9 (4) | C226—C225—C224—C223 | 1.0 (8) |
Pd2—P2—C211—C216 | 134.6 (3) | C122—C121—C126—C125 | 0.2 (6) |
C111—C112—C113—C114 | −1.4 (7) | P1—C121—C126—C125 | −179.8 (4) |
C232—C231—C236—C235 | −0.2 (6) | C123—C124—C125—C126 | −0.5 (8) |
P2—C231—C236—C235 | −179.2 (4) | C121—C126—C125—C124 | 0.2 (7) |
C226—C221—C222—C223 | 1.4 (7) | C216—C215—C214—C213 | −1.0 (9) |
P2—C221—C222—C223 | −177.8 (3) | C212—C213—C214—C215 | 3.3 (8) |
C112—C113—C114—C115 | 3.0 (7) | C131—C132—C133—C134 | 0.5 (9) |
C113—C112—C111—C116 | −1.3 (7) | C135—C134—C133—C132 | −1.3 (9) |
C113—C112—C111—P1 | −176.9 (4) | C233—C234—C235—C236 | −0.3 (8) |
C131—P1—C111—C112 | −124.2 (4) | C231—C236—C235—C234 | 0.1 (7) |
C121—P1—C111—C112 | 124.7 (4) | C235—C234—C233—C232 | 0.5 (8) |
Pd1—P1—C111—C112 | −5.2 (4) | C231—C232—C233—C234 | −0.6 (8) |
C131—P1—C111—C116 | 60.3 (4) | C114—C115—C116—C111 | −0.7 (7) |
C121—P1—C111—C116 | −50.8 (4) | C112—C111—C116—C115 | 2.3 (6) |
Pd1—P1—C111—C116 | 179.3 (3) | P1—C111—C116—C115 | 178.0 (4) |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+2, −y, −z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C235—H235···Cl2iii | 0.93 | 2.80 | 3.637 (6) | 151 |
C123—H123···Cg1iv | 0.93 | 2.91 | 3.762 (7) | 153 |
C114—H114···Cg2iv | 0.93 | 2.89 | 3.705 (5) | 147 |
Symmetry codes: (iii) x−1, y, z; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [PdCl2(C18H15P)2] |
Mr | 701.84 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 9.9830 (3), 11.3023 (3), 15.6037 (5) |
α, β, γ (°) | 89.947 (2), 89.539 (1), 63.926 (1) |
V (Å3) | 1581.34 (8) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.88 |
Crystal size (mm) | 0.12 × 0.09 × 0.04 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Gaussian (Coppens et al., 1965) |
Tmin, Tmax | 0.891, 0.962 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27320, 7114, 4370 |
Rint | 0.073 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.046, 0.128, 1.01 |
No. of reflections | 7114 |
No. of parameters | 373 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.92, −0.92 |
Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and Mercury (Macrae et al., 2006), WinGX (Farrugia, 1999).
Pd1—Cl1 | 2.2996 (11) | Pd2—Cl2 | 2.2950 (11) |
Pd1—P1 | 2.3247 (10) | Pd2—P2 | 2.3540 (10) |
Cl1—Pd1—P1 | 92.41 (4) | Cl2—Pd2—P2 | 88.31 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C235—H235···Cl2i | 0.93 | 2.80 | 3.637 (6) | 151 |
C123—H123···Cg1ii | 0.93 | 2.91 | 3.762 (7) | 153 |
C114—H114···Cg2ii | 0.93 | 2.89 | 3.705 (5) | 147 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1, −y, −z+1. |
We have previously investigated polymorphism in molecular compounds and in active pharmaceutical ingredients (APIs) (Landre et al., 2010; Martins et al., 2009; Corrêa et al., 2006). Accordingly, as part of our ongoing effort to investigate this phenomenon in molecular crystals, we have also studied polymorphism in transition metal complexes. The complex studied here, trans-[PdCl2(PPh3)2], is commonly used as a palladium precursor in inorganic synthesis in order to obtain new derivatives presenting catalytic (Dileep & Bhat, 2010) and biological activities (Shaheen et al., 2010).
This complex has previously been reported in two polymorphic forms: form (I), space group P1 (Ferguson et al., 1982) [with unit-cell parameters a = 9.69 (2), b = 10.325 (2), c = 9.194 (1) Å, α = 91.38 (1), β = 111.94 (1), γ = 72.51 (1)°]; and form (II), space group P21/c (Pons et al., 2008) [with unit-cell parameters a = 9.296 (5), b = 19.889 (8), c = 10.621 (6) Å, β = 121.71 (4)°]. In addition, four solvate forms are also known with p-dichlorobenzene (Kitano et al., 1983), chloroform (Stark & Whitmire, 1997), dichloromethane (Oilunkaniemi et al., 2003) and dichloroethane (Steyl, 2006). In the chloroform, dichloromethane and dichloroethane solvates the Pd atom lies on an inversion centre.
We report here a new polymorphic form [form (III)] of the title compound, with two independent molecules (hereafter called molecule 1 and molecule 2, Fig. 1) of the complex in the triclinic cell; in each case the palladium atom is located on a crystallographic inversion centre. With the Pd atom of each molecule lying on independent inversion centres, a square-planar coordination of the PdII metal centre is observed, with principal geometry details given in Table 1. These dimensions are in accord with those found for related complexes, including forms (I) and (II) (Ferguson et al., 1982; Pons et al. 2008) and their solvate forms previously reported (Kitano et al., 1983; Stark & Whitmire, 1997; Oilunkaniemi et al., 2003; Steyl, 2006).
In molecule 1, trans-chloride ligands are in an eclipsed conformation relative to the triphenylphosphane ligands, with the Cl1—Pd1—P1—C121 torsion angle near zero [1.09 (19)°], whereas in molecule 2, a gauche conformation is present with a Cl2—Pd2—P2—C221 torsion angle of -32.25 (17)° and this is the main difference between them (Fig. 1).
In the crystal structure there are C—H···Cl non-classical intermolecular interactions (see Table 2) involving the chlorine atoms of molecule 2 and adjacent symmetry-related aromatic C—H groups, giving rise to an extended chain in the [100] direction (Fig. 2). In other crystal structures of trans-[PdCl2(PPh3)2], the chlorine atoms are involved in hydrogen bonding and as a consequence twisted conformations are observed with non-zero Cl—Pd—P—C torsion angles in the range of 12.77 (10) to 17.00 (23)° (Ferguson et al., 1982; Kitano et al., 1983; Stark & Whitmire, 1997; Oilunkaniemi et al., 2003; Steyl, 2006; Pons et al., 2008). Comparisons among these crystalline forms of trans-[PdCl2(PPh3)2] and the respective molecular conformations of each structure suggest that the C—H···Cl—Pd intermolecular interactions are important in establishing the conformation and crystalline form. The absence of C—H···Cl—Pd intermolecular interactions in molecule 1 and their presence in molecule 2 contribute to the existence of two conformations giving rise to this new polymorphic form. Further C—H···π interactions (see Table 2) and van der Waals contacts play a role in the crystal assembly of the new form (III), and give rise to the two independent layers formed by molecules 1 and 2 in form (III) (Fig. 3).