Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012741/cm6046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012741/cm6046Isup2.hkl |
CCDC reference: 217427
All chemicals were purchased from Aldrich and used without further purification. Solvents were dried and degassed using appropriate methods. Standard Schlenk line techniques were also employed. [Pd(η3-allyl)Cl2] (35 mg, 0.096 mmol) was dissolved in tetrahydrofuran (THF, 10 ml), followed by the addition of AgCF3SO3 (53 mg, 0.21 mmol). The resulting solution was stirred at ambient temperature after which it was filtered in order to remove AgCl. (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (129 mg, 0.20 mmol) was added to the filtrate and the solution was stirred for 30 min. The addition of ca 20 ml of hexane led to precipitation of the title compound, which was filtered off and washed with hexane (two times ca 20 ml) and diethylether (two times ca 20 ml). The compound was then dried in vacuo to form a white powder (165 mg, 90% yield). Crystals suitable for X-Ray diffraction analysis were obtained using recrystallization methods from a CH2Cl2/Et2O/MeOH solution. 1H NMR (CDCl3): 3.10 (m, CH2, 2H), 4.10 (m, CH2, 2H), 5.92 (m,CH, 1H), 6.40–7.80 (m, Ph, 32H). 13C NMR (CDCl3): 65.9 (CH2, allyl); 123.5 (CH, allyl); 126–133 (Ph). 31P NMR (CDCl3): 22.2 (d, J = 50 Hz); 23.3 (d, J = 50 Hz).
All H atoms were placed at calculated positions and allowed to ride during subsequent refinement, with Uiso(H) = 1.2Ueq(C). The allyl ligand was found to be disordered: the middle C atom has been modelled with variable occupancy factors over two different positions, C46 and C46', and found to have occupancy rates of 52 and 48%, respectively. A total of 3491 estimated Friedel pairs have not been merged and were also used as independent data for structure refinement.
Data collection: COLLECT (Nonius 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare at al., 1994); program(s) used to refine structure: SHELXTL (Bruker 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
[Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2 | F(000) = 2040 |
Mr = 1004.10 | Dx = 1.484 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 19214 reflections |
a = 11.1814 (3) Å | θ = 1.0–25.0° |
b = 19.7359 (4) Å | µ = 0.70 mm−1 |
c = 20.3672 (4) Å | T = 180 K |
V = 4494.53 (18) Å3 | Block, colourless |
Z = 4 | 0.12 × 0.10 × 0.07 mm |
Nonius KappaCCD diffractometer | 6903 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.064 |
Thin–slice ω and ϕ scans | θmax = 25.0°, θmin = 3.6° |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | h = −11→13 |
Tmin = 0.898, Tmax = 0.961 | k = −23→23 |
29207 measured reflections | l = −24→24 |
7894 independent 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)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.075 | w = 1/[σ2(Fo2) + (0.0146P)2 + 4.6523P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max = 0.001 |
7894 reflections | Δρmax = 0.36 e Å−3 |
560 parameters | Δρmin = −0.42 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 3491 Friedel reflections |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (2) |
[Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2 | V = 4494.53 (18) Å3 |
Mr = 1004.10 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 11.1814 (3) Å | µ = 0.70 mm−1 |
b = 19.7359 (4) Å | T = 180 K |
c = 20.3672 (4) Å | 0.12 × 0.10 × 0.07 mm |
Nonius KappaCCD diffractometer | 7894 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 6903 reflections with I > 2σ(I) |
Tmin = 0.898, Tmax = 0.961 | Rint = 0.064 |
29207 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | H-atom parameters constrained |
wR(F2) = 0.075 | Δρmax = 0.36 e Å−3 |
S = 1.05 | Δρmin = −0.42 e Å−3 |
7894 reflections | Absolute structure: Flack (1983), 3491 Friedel reflections |
560 parameters | Absolute structure parameter: −0.03 (2) |
0 restraints |
Experimental. The allyl ligand (CH2—CH—CH2 -> C45—C46—C47) was found to have C46 disordered over two different positions. Thus, the atom was modelled with variable occupancy factors over two different positions, C46 and C46', and found to have occupancy rates of 52% and 48%, respectively. Terminal atoms from the same ligand (C45 and C47) are also slightly affected by thermal disorder (large Ueq when compared to the neighbours). The crystallization solvent molecule (dichloromethane) and the trifluoromethanesulfonate anion are slightly disordered in the crystal structure, with this being reflected in the large anisotropic displacement 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 | Occ. (<1) | |
Pd1 | 0.76466 (3) | 0.766378 (14) | 0.109135 (14) | 0.02748 (8) | |
P1 | 0.81180 (9) | 0.81691 (5) | 0.20768 (5) | 0.0263 (2) | |
P2 | 0.60009 (10) | 0.70856 (5) | 0.14722 (5) | 0.0251 (2) | |
C1 | 0.8986 (4) | 0.89401 (19) | 0.1939 (2) | 0.0273 (9) | |
C2 | 0.8663 (4) | 0.9358 (2) | 0.1414 (2) | 0.0370 (11) | |
H2 | 0.7974 | 0.9253 | 0.1161 | 0.044* | |
C3 | 0.9335 (4) | 0.9920 (2) | 0.1260 (2) | 0.0430 (12) | |
H3 | 0.9103 | 1.0203 | 0.0905 | 0.052* | |
C4 | 1.0335 (4) | 1.0073 (2) | 0.1615 (3) | 0.0435 (13) | |
H4 | 1.0802 | 1.0459 | 0.1505 | 0.052* | |
C5 | 1.0664 (4) | 0.9669 (2) | 0.2133 (2) | 0.0415 (11) | |
H5 | 1.1360 | 0.9777 | 0.2379 | 0.050* | |
C6 | 0.9992 (4) | 0.9102 (2) | 0.2301 (2) | 0.0335 (10) | |
H6 | 1.0222 | 0.8828 | 0.2662 | 0.040* | |
C7 | 0.8965 (3) | 0.7675 (2) | 0.2668 (2) | 0.0303 (9) | |
C8 | 0.9031 (4) | 0.7863 (2) | 0.3322 (2) | 0.0378 (11) | |
H8 | 0.8635 | 0.8261 | 0.3470 | 0.045* | |
C9 | 0.9684 (4) | 0.7466 (2) | 0.3763 (2) | 0.0489 (14) | |
H9 | 0.9725 | 0.7591 | 0.4213 | 0.059* | |
C10 | 1.0265 (5) | 0.6897 (2) | 0.3547 (3) | 0.0561 (15) | |
H10 | 1.0712 | 0.6629 | 0.3848 | 0.067* | |
C11 | 1.0201 (5) | 0.6710 (2) | 0.2894 (3) | 0.0550 (15) | |
H11 | 1.0609 | 0.6316 | 0.2746 | 0.066* | |
C12 | 0.9550 (4) | 0.7094 (2) | 0.2458 (2) | 0.0389 (11) | |
H12 | 0.9499 | 0.6960 | 0.2011 | 0.047* | |
C13 | 0.6753 (4) | 0.84474 (19) | 0.25022 (19) | 0.0259 (9) | |
C14 | 0.6455 (4) | 0.9147 (2) | 0.2488 (2) | 0.0347 (11) | |
H14 | 0.7013 | 0.9463 | 0.2314 | 0.042* | |
C15 | 0.5384 (4) | 0.9373 (2) | 0.2718 (2) | 0.0367 (11) | |
H15 | 0.5205 | 0.9843 | 0.2702 | 0.044* | |
C16 | 0.4543 (4) | 0.8923 (2) | 0.2978 (2) | 0.0305 (10) | |
C17 | 0.3404 (4) | 0.9146 (2) | 0.3200 (2) | 0.0362 (11) | |
H17 | 0.3202 | 0.9612 | 0.3168 | 0.043* | |
C18 | 0.2592 (4) | 0.8697 (2) | 0.34579 (19) | 0.0365 (10) | |
H18 | 0.1832 | 0.8854 | 0.3602 | 0.044* | |
C19 | 0.2883 (4) | 0.8010 (2) | 0.35093 (19) | 0.0353 (10) | |
H19 | 0.2321 | 0.7703 | 0.3694 | 0.042* | |
C20 | 0.3974 (4) | 0.7773 (2) | 0.32960 (19) | 0.0309 (9) | |
H20 | 0.4158 | 0.7305 | 0.3337 | 0.037* | |
C21 | 0.4827 (4) | 0.82185 (19) | 0.30170 (19) | 0.0264 (9) | |
C22 | 0.5958 (4) | 0.79839 (18) | 0.27717 (19) | 0.0234 (9) | |
C23 | 0.6240 (3) | 0.72433 (18) | 0.28473 (18) | 0.0226 (8) | |
C24 | 0.6512 (4) | 0.69948 (19) | 0.3492 (2) | 0.0276 (9) | |
C25 | 0.6551 (4) | 0.7420 (2) | 0.40560 (18) | 0.0350 (10) | |
H25 | 0.6395 | 0.7891 | 0.4009 | 0.042* | |
C26 | 0.6808 (4) | 0.7164 (2) | 0.4665 (2) | 0.0446 (12) | |
H26 | 0.6824 | 0.7456 | 0.5035 | 0.053* | |
C27 | 0.7046 (5) | 0.6472 (2) | 0.4743 (2) | 0.0510 (14) | |
H27 | 0.7236 | 0.6299 | 0.5166 | 0.061* | |
C28 | 0.7010 (4) | 0.6047 (2) | 0.4223 (2) | 0.0422 (12) | |
H28 | 0.7168 | 0.5578 | 0.4284 | 0.051* | |
C29 | 0.6739 (4) | 0.6293 (2) | 0.3590 (2) | 0.0298 (9) | |
C30 | 0.6693 (4) | 0.5859 (2) | 0.3039 (2) | 0.0318 (10) | |
H30 | 0.6846 | 0.5389 | 0.3095 | 0.038* | |
C31 | 0.6438 (4) | 0.60986 (19) | 0.2436 (2) | 0.0269 (10) | |
H31 | 0.6412 | 0.5792 | 0.2076 | 0.032* | |
C32 | 0.6207 (3) | 0.67951 (19) | 0.23235 (19) | 0.0248 (9) | |
C33 | 0.6767 (4) | 0.5960 (2) | 0.0793 (2) | 0.0368 (11) | |
H33 | 0.7534 | 0.6158 | 0.0852 | 0.044* | |
C34 | 0.6670 (5) | 0.5343 (2) | 0.0473 (2) | 0.0457 (12) | |
H34 | 0.7365 | 0.5123 | 0.0310 | 0.055* | |
C35 | 0.5564 (5) | 0.5049 (2) | 0.0393 (2) | 0.0488 (14) | |
H35 | 0.5502 | 0.4619 | 0.0186 | 0.059* | |
C36 | 0.4549 (5) | 0.5371 (2) | 0.0610 (2) | 0.0484 (13) | |
H36 | 0.3787 | 0.5168 | 0.0545 | 0.058* | |
C37 | 0.4639 (4) | 0.6003 (2) | 0.0928 (2) | 0.0360 (11) | |
H37 | 0.3939 | 0.6230 | 0.1075 | 0.043* | |
C38 | 0.5764 (4) | 0.62941 (19) | 0.1027 (2) | 0.0307 (9) | |
C39 | 0.4632 (3) | 0.7574 (2) | 0.14657 (18) | 0.0281 (9) | |
C40 | 0.3583 (4) | 0.7359 (2) | 0.1764 (2) | 0.0371 (10) | |
H40 | 0.3565 | 0.6935 | 0.1984 | 0.045* | |
C41 | 0.2560 (4) | 0.7757 (3) | 0.1744 (2) | 0.0494 (12) | |
H41 | 0.1838 | 0.7600 | 0.1937 | 0.059* | |
C42 | 0.2598 (5) | 0.8381 (2) | 0.1441 (2) | 0.0493 (12) | |
H42 | 0.1902 | 0.8657 | 0.1434 | 0.059* | |
C43 | 0.3623 (4) | 0.8607 (2) | 0.1154 (2) | 0.0437 (11) | |
H43 | 0.3636 | 0.9038 | 0.0947 | 0.052* | |
C44 | 0.4651 (4) | 0.82081 (19) | 0.1161 (2) | 0.0334 (9) | |
H44 | 0.5364 | 0.8367 | 0.0960 | 0.040* | |
C45 | 0.7445 (5) | 0.7431 (3) | 0.00591 (19) | 0.0515 (12) | |
H45A | 0.7785 | 0.6994 | −0.0090 | 0.062* | 0.52 (2) |
H45B | 0.6655 | 0.7532 | −0.0137 | 0.062* | 0.52 (2) |
H45C | 0.7211 | 0.6960 | −0.0050 | 0.062* | 0.48 (2) |
H45D | 0.7036 | 0.7776 | −0.0213 | 0.062* | 0.48 (2) |
C46 | 0.8204 (12) | 0.7947 (9) | 0.0105 (4) | 0.043 (4) | 0.52 (2) |
H46A | 0.7866 | 0.8388 | −0.0049 | 0.051* | 0.52 (2) |
C46' | 0.8574 (13) | 0.7534 (9) | 0.0180 (6) | 0.045 (4) | 0.48 (2) |
H46B | 0.9041 | 0.7102 | 0.0172 | 0.054* | 0.48 (2) |
C47 | 0.9142 (5) | 0.8012 (3) | 0.0497 (3) | 0.0576 (15) | |
H47A | 0.9422 | 0.8481 | 0.0580 | 0.069* | 0.52 (2) |
H47B | 0.9802 | 0.7685 | 0.0430 | 0.069* | 0.52 (2) |
H47C | 0.9079 | 0.8476 | 0.0315 | 0.069* | 0.48 (2) |
H47D | 0.9953 | 0.7899 | 0.0659 | 0.069* | 0.48 (2) |
S2 | 1.05159 (15) | 0.56823 (8) | 0.03748 (8) | 0.0630 (4) | |
O1 | 1.1652 (4) | 0.5641 (2) | 0.0060 (2) | 0.0815 (13) | |
O2 | 0.9618 (4) | 0.5271 (3) | 0.0066 (3) | 0.1098 (18) | |
O3 | 1.0093 (6) | 0.6334 (2) | 0.0557 (3) | 0.127 (2) | |
C48 | 1.0739 (9) | 0.5289 (4) | 0.1150 (5) | 0.111 (3) | |
F1 | 0.9739 (7) | 0.5311 (3) | 0.1509 (3) | 0.184 (3) | |
F2 | 1.1555 (6) | 0.5575 (4) | 0.1504 (3) | 0.181 (3) | |
F3 | 1.1053 (7) | 0.4656 (3) | 0.1093 (3) | 0.197 (3) | |
C49 | 1.1250 (7) | 0.4243 (4) | −0.0829 (5) | 0.126 (4) | |
H49A | 1.1397 | 0.4724 | −0.0716 | 0.151* | |
H49B | 1.0385 | 0.4155 | −0.0773 | 0.151* | |
Cl1 | 1.2034 (3) | 0.37380 (13) | −0.02904 (14) | 0.1829 (16) | |
Cl2 | 1.16292 (17) | 0.41149 (8) | −0.16415 (12) | 0.0988 (7) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd1 | 0.02915 (16) | 0.02861 (14) | 0.02467 (14) | −0.00132 (13) | 0.00557 (14) | 0.00032 (13) |
P1 | 0.0251 (6) | 0.0244 (5) | 0.0295 (6) | −0.0023 (4) | 0.0016 (5) | 0.0016 (4) |
P2 | 0.0275 (6) | 0.0266 (5) | 0.0212 (5) | 0.0008 (4) | 0.0005 (5) | −0.0017 (4) |
C1 | 0.024 (2) | 0.025 (2) | 0.033 (2) | 0.0003 (17) | 0.0055 (19) | −0.0020 (17) |
C2 | 0.035 (3) | 0.033 (2) | 0.043 (3) | 0.0001 (19) | 0.001 (2) | 0.003 (2) |
C3 | 0.041 (3) | 0.034 (2) | 0.054 (3) | 0.000 (2) | 0.015 (2) | 0.010 (2) |
C4 | 0.039 (3) | 0.029 (2) | 0.063 (4) | −0.005 (2) | 0.022 (3) | −0.001 (2) |
C5 | 0.035 (3) | 0.036 (3) | 0.053 (3) | −0.005 (2) | 0.006 (2) | −0.006 (2) |
C6 | 0.034 (3) | 0.031 (2) | 0.035 (3) | −0.0030 (19) | 0.001 (2) | −0.0032 (18) |
C7 | 0.022 (2) | 0.029 (2) | 0.040 (3) | −0.006 (2) | 0.0011 (17) | 0.005 (2) |
C8 | 0.033 (3) | 0.037 (3) | 0.044 (3) | −0.0032 (19) | −0.005 (2) | 0.004 (2) |
C9 | 0.039 (3) | 0.061 (4) | 0.046 (3) | −0.010 (2) | −0.010 (2) | 0.019 (2) |
C10 | 0.047 (3) | 0.038 (3) | 0.083 (4) | −0.004 (2) | −0.020 (3) | 0.029 (3) |
C11 | 0.044 (3) | 0.035 (3) | 0.086 (5) | 0.003 (2) | −0.005 (3) | 0.012 (3) |
C12 | 0.037 (3) | 0.030 (2) | 0.050 (3) | −0.0004 (19) | 0.001 (2) | 0.005 (2) |
C13 | 0.026 (2) | 0.028 (2) | 0.024 (2) | 0.0020 (17) | −0.0007 (18) | −0.0003 (16) |
C14 | 0.036 (3) | 0.026 (2) | 0.041 (3) | −0.0056 (19) | 0.003 (2) | −0.0007 (19) |
C15 | 0.044 (3) | 0.021 (2) | 0.045 (3) | 0.002 (2) | 0.004 (2) | 0.0019 (19) |
C16 | 0.031 (2) | 0.032 (2) | 0.029 (2) | 0.0005 (19) | −0.0044 (19) | −0.0056 (18) |
C17 | 0.039 (3) | 0.038 (3) | 0.032 (2) | 0.010 (2) | −0.003 (2) | −0.0044 (19) |
C18 | 0.027 (2) | 0.052 (3) | 0.031 (2) | 0.007 (2) | 0.004 (2) | −0.0040 (18) |
C19 | 0.033 (3) | 0.046 (3) | 0.027 (2) | −0.0052 (19) | 0.0085 (19) | −0.0011 (18) |
C20 | 0.036 (2) | 0.031 (2) | 0.026 (2) | −0.0002 (19) | 0.0075 (18) | 0.0007 (18) |
C21 | 0.032 (2) | 0.023 (2) | 0.024 (2) | −0.0001 (18) | −0.0003 (18) | −0.0038 (16) |
C22 | 0.027 (2) | 0.023 (2) | 0.020 (2) | −0.0028 (17) | −0.0009 (17) | −0.0042 (16) |
C23 | 0.0206 (19) | 0.023 (2) | 0.024 (2) | 0.0014 (16) | 0.0028 (16) | 0.0014 (17) |
C24 | 0.024 (2) | 0.028 (2) | 0.031 (2) | −0.0054 (17) | 0.0008 (18) | 0.0013 (18) |
C25 | 0.037 (2) | 0.038 (2) | 0.030 (2) | −0.003 (2) | 0.0029 (18) | −0.0033 (18) |
C26 | 0.061 (3) | 0.050 (3) | 0.023 (2) | −0.003 (2) | −0.004 (2) | −0.0045 (19) |
C27 | 0.071 (4) | 0.055 (3) | 0.027 (3) | 0.004 (3) | −0.003 (2) | 0.013 (2) |
C28 | 0.052 (3) | 0.042 (3) | 0.033 (3) | 0.005 (2) | −0.004 (2) | 0.009 (2) |
C29 | 0.029 (2) | 0.029 (2) | 0.032 (2) | 0.0001 (18) | −0.002 (2) | 0.0045 (18) |
C30 | 0.030 (2) | 0.025 (2) | 0.040 (3) | 0.0048 (18) | 0.004 (2) | −0.0005 (18) |
C31 | 0.028 (2) | 0.023 (2) | 0.029 (2) | −0.0038 (17) | 0.0029 (19) | 0.0012 (17) |
C32 | 0.022 (2) | 0.029 (2) | 0.024 (2) | −0.0010 (17) | 0.0035 (17) | 0.0009 (17) |
C33 | 0.037 (3) | 0.043 (3) | 0.031 (2) | 0.000 (2) | 0.005 (2) | −0.0044 (19) |
C34 | 0.064 (3) | 0.040 (3) | 0.033 (3) | 0.012 (2) | −0.001 (2) | −0.011 (2) |
C35 | 0.076 (4) | 0.029 (3) | 0.042 (3) | 0.004 (3) | −0.024 (3) | −0.014 (2) |
C36 | 0.056 (3) | 0.040 (3) | 0.049 (3) | −0.009 (2) | −0.016 (3) | −0.003 (2) |
C37 | 0.039 (3) | 0.031 (2) | 0.037 (3) | −0.0012 (19) | −0.006 (2) | −0.0001 (19) |
C38 | 0.041 (2) | 0.031 (2) | 0.020 (2) | −0.0010 (18) | −0.003 (2) | 0.0008 (18) |
C39 | 0.029 (2) | 0.034 (2) | 0.021 (2) | 0.0028 (18) | −0.0017 (17) | −0.0066 (17) |
C40 | 0.035 (2) | 0.048 (2) | 0.028 (2) | −0.002 (2) | 0.0012 (18) | −0.004 (2) |
C41 | 0.031 (3) | 0.081 (3) | 0.037 (2) | 0.009 (3) | 0.004 (2) | −0.015 (2) |
C42 | 0.043 (3) | 0.063 (3) | 0.042 (3) | 0.027 (3) | −0.010 (3) | −0.016 (2) |
C43 | 0.052 (3) | 0.043 (3) | 0.036 (3) | 0.015 (2) | −0.008 (3) | −0.004 (2) |
C44 | 0.043 (3) | 0.031 (2) | 0.026 (2) | 0.0020 (19) | −0.001 (2) | −0.0053 (19) |
C45 | 0.064 (3) | 0.069 (3) | 0.021 (2) | −0.005 (3) | 0.013 (2) | −0.0043 (19) |
C46 | 0.056 (7) | 0.046 (8) | 0.027 (5) | −0.001 (6) | 0.012 (5) | 0.009 (5) |
C46' | 0.050 (8) | 0.048 (10) | 0.037 (6) | −0.002 (6) | 0.010 (5) | −0.002 (5) |
C47 | 0.063 (4) | 0.064 (4) | 0.047 (3) | −0.012 (3) | 0.029 (3) | 0.007 (3) |
S2 | 0.0633 (11) | 0.0567 (9) | 0.0691 (11) | 0.0066 (8) | 0.0052 (8) | 0.0198 (7) |
O1 | 0.062 (3) | 0.098 (3) | 0.084 (3) | −0.019 (2) | 0.015 (2) | 0.007 (2) |
O2 | 0.059 (3) | 0.149 (5) | 0.122 (4) | −0.025 (3) | −0.007 (3) | −0.008 (4) |
O3 | 0.196 (6) | 0.062 (3) | 0.123 (5) | 0.045 (3) | 0.023 (4) | 0.016 (3) |
C48 | 0.131 (8) | 0.104 (6) | 0.098 (7) | 0.037 (6) | 0.011 (7) | 0.043 (6) |
F1 | 0.208 (7) | 0.222 (7) | 0.122 (4) | 0.037 (5) | 0.083 (5) | 0.088 (4) |
F2 | 0.166 (6) | 0.287 (9) | 0.089 (4) | 0.042 (6) | −0.046 (4) | −0.016 (4) |
F3 | 0.338 (9) | 0.106 (4) | 0.147 (5) | 0.089 (5) | 0.028 (6) | 0.066 (4) |
C49 | 0.062 (5) | 0.097 (6) | 0.220 (11) | 0.013 (4) | −0.002 (6) | −0.067 (6) |
Cl1 | 0.269 (4) | 0.1246 (18) | 0.155 (2) | 0.112 (2) | 0.100 (2) | 0.0565 (16) |
Cl2 | 0.0806 (13) | 0.0549 (10) | 0.161 (2) | −0.0108 (9) | −0.0249 (13) | 0.0050 (10) |
Pd1—C46' | 2.141 (10) | C26—C27 | 1.401 (6) |
Pd1—C45 | 2.164 (4) | C26—H26 | 0.9500 |
Pd1—C47 | 2.176 (5) | C27—C28 | 1.352 (6) |
Pd1—C46 | 2.177 (9) | C27—H27 | 0.9500 |
Pd1—P2 | 2.3000 (11) | C28—C29 | 1.411 (6) |
Pd1—P1 | 2.3023 (11) | C28—H28 | 0.9500 |
P1—C7 | 1.815 (4) | C29—C30 | 1.411 (6) |
P1—C1 | 1.827 (4) | C30—C31 | 1.347 (6) |
P1—C13 | 1.839 (4) | C30—H30 | 0.9500 |
P2—C39 | 1.809 (4) | C31—C32 | 1.417 (5) |
P2—C38 | 1.825 (4) | C31—H31 | 0.9500 |
P2—C32 | 1.840 (4) | C33—C38 | 1.386 (6) |
C1—C6 | 1.382 (6) | C33—C34 | 1.386 (6) |
C1—C2 | 1.398 (6) | C33—H33 | 0.9500 |
C2—C3 | 1.376 (6) | C34—C35 | 1.375 (7) |
C2—H2 | 0.9500 | C34—H34 | 0.9500 |
C3—C4 | 1.366 (7) | C35—C36 | 1.374 (7) |
C3—H3 | 0.9500 | C35—H35 | 0.9500 |
C4—C5 | 1.373 (6) | C36—C37 | 1.410 (6) |
C4—H4 | 0.9500 | C36—H36 | 0.9500 |
C5—C6 | 1.390 (6) | C37—C38 | 1.397 (6) |
C5—H5 | 0.9500 | C37—H37 | 0.9500 |
C6—H6 | 0.9500 | C39—C40 | 1.387 (6) |
C7—C8 | 1.384 (6) | C39—C44 | 1.397 (5) |
C7—C12 | 1.388 (6) | C40—C41 | 1.388 (6) |
C8—C9 | 1.398 (6) | C40—H40 | 0.9500 |
C8—H8 | 0.9500 | C41—C42 | 1.378 (6) |
C9—C10 | 1.370 (7) | C41—H41 | 0.9500 |
C9—H9 | 0.9500 | C42—C43 | 1.362 (7) |
C10—C11 | 1.383 (7) | C42—H42 | 0.9500 |
C10—H10 | 0.9500 | C43—C44 | 1.394 (6) |
C11—C12 | 1.376 (6) | C43—H43 | 0.9500 |
C11—H11 | 0.9500 | C44—H44 | 0.9500 |
C12—H12 | 0.9500 | C45—C46' | 1.303 (14) |
C13—C22 | 1.389 (5) | C45—C46 | 1.330 (13) |
C13—C14 | 1.420 (5) | C45—H45A | 0.9900 |
C14—C15 | 1.362 (6) | C45—H45B | 0.9900 |
C14—H14 | 0.9500 | C45—H45C | 0.9900 |
C15—C16 | 1.398 (6) | C45—H45D | 0.9900 |
C15—H15 | 0.9500 | C46—C47 | 1.325 (13) |
C16—C17 | 1.420 (6) | C46—H46A | 1.0000 |
C16—C21 | 1.428 (5) | C46'—C47 | 1.308 (13) |
C17—C18 | 1.373 (6) | C46'—H46B | 1.0000 |
C17—H17 | 0.9500 | C47—H47A | 0.9900 |
C18—C19 | 1.399 (6) | C47—H47B | 0.9900 |
C18—H18 | 0.9500 | C47—H47C | 0.9900 |
C19—C20 | 1.378 (6) | C47—H47D | 0.9900 |
C19—H19 | 0.9500 | S2—O3 | 1.419 (5) |
C20—C21 | 1.415 (5) | S2—O1 | 1.425 (4) |
C20—H20 | 0.9500 | S2—O2 | 1.436 (5) |
C21—C22 | 1.436 (6) | S2—C48 | 1.777 (8) |
C22—C23 | 1.503 (5) | C48—F2 | 1.293 (11) |
C23—C32 | 1.386 (5) | C48—F3 | 1.302 (9) |
C23—C24 | 1.434 (5) | C48—F1 | 1.335 (9) |
C24—C29 | 1.423 (5) | C49—Cl1 | 1.722 (9) |
C24—C25 | 1.424 (5) | C49—Cl2 | 1.727 (9) |
C25—C26 | 1.370 (6) | C49—H49A | 0.9900 |
C25—H25 | 0.9500 | C49—H49B | 0.9900 |
C46'—Pd1—C45 | 35.2 (4) | C30—C29—C24 | 118.2 (4) |
C46'—Pd1—C47 | 35.3 (3) | C31—C30—C29 | 121.3 (4) |
C45—Pd1—C47 | 66.9 (2) | C31—C30—H30 | 119.3 |
C46'—Pd1—C46 | 24.7 (3) | C29—C30—H30 | 119.3 |
C45—Pd1—C46 | 35.7 (3) | C30—C31—C32 | 121.7 (4) |
C47—Pd1—C46 | 35.4 (3) | C30—C31—H31 | 119.1 |
C46'—Pd1—P2 | 128.4 (3) | C32—C31—H31 | 119.1 |
C45—Pd1—P2 | 97.97 (14) | C23—C32—C31 | 119.3 (4) |
C47—Pd1—P2 | 163.61 (15) | C23—C32—P2 | 122.0 (3) |
C46—Pd1—P2 | 131.9 (3) | C31—C32—P2 | 118.5 (3) |
C46'—Pd1—P1 | 134.1 (3) | C38—C33—C34 | 121.1 (4) |
C45—Pd1—P1 | 164.35 (14) | C38—C33—H33 | 119.5 |
C47—Pd1—P1 | 99.90 (16) | C34—C33—H33 | 119.5 |
C46—Pd1—P1 | 128.9 (3) | C35—C34—C33 | 119.8 (5) |
P2—Pd1—P1 | 95.97 (4) | C35—C34—H34 | 120.1 |
C7—P1—C1 | 105.78 (19) | C33—C34—H34 | 120.1 |
C7—P1—C13 | 106.29 (18) | C36—C35—C34 | 120.6 (4) |
C1—P1—C13 | 105.36 (18) | C36—C35—H35 | 119.7 |
C7—P1—Pd1 | 117.73 (15) | C34—C35—H35 | 119.7 |
C1—P1—Pd1 | 110.38 (14) | C35—C36—C37 | 119.9 (5) |
C13—P1—Pd1 | 110.50 (13) | C35—C36—H36 | 120.1 |
C39—P2—C38 | 109.24 (18) | C37—C36—H36 | 120.1 |
C39—P2—C32 | 106.18 (18) | C38—C37—C36 | 119.6 (4) |
C38—P2—C32 | 102.67 (18) | C38—C37—H37 | 120.2 |
C39—P2—Pd1 | 114.22 (13) | C36—C37—H37 | 120.2 |
C38—P2—Pd1 | 111.91 (14) | C33—C38—C37 | 118.9 (4) |
C32—P2—Pd1 | 111.86 (13) | C33—C38—P2 | 117.4 (3) |
C6—C1—C2 | 118.8 (4) | C37—C38—P2 | 123.6 (3) |
C6—C1—P1 | 122.9 (3) | C40—C39—C44 | 118.8 (4) |
C2—C1—P1 | 118.1 (3) | C40—C39—P2 | 123.3 (3) |
C3—C2—C1 | 120.5 (4) | C44—C39—P2 | 117.9 (3) |
C3—C2—H2 | 119.7 | C39—C40—C41 | 120.7 (4) |
C1—C2—H2 | 119.7 | C39—C40—H40 | 119.6 |
C4—C3—C2 | 120.3 (4) | C41—C40—H40 | 119.6 |
C4—C3—H3 | 119.8 | C42—C41—C40 | 119.5 (5) |
C2—C3—H3 | 119.8 | C42—C41—H41 | 120.2 |
C3—C4—C5 | 119.8 (4) | C40—C41—H41 | 120.2 |
C3—C4—H4 | 120.1 | C43—C42—C41 | 120.8 (4) |
C5—C4—H4 | 120.1 | C43—C42—H42 | 119.6 |
C4—C5—C6 | 120.8 (4) | C41—C42—H42 | 119.6 |
C4—C5—H5 | 119.6 | C42—C43—C44 | 120.3 (4) |
C6—C5—H5 | 119.6 | C42—C43—H43 | 119.9 |
C1—C6—C5 | 119.7 (4) | C44—C43—H43 | 119.9 |
C1—C6—H6 | 120.1 | C43—C44—C39 | 119.9 (4) |
C5—C6—H6 | 120.1 | C43—C44—H44 | 120.1 |
C8—C7—C12 | 119.5 (4) | C39—C44—H44 | 120.1 |
C8—C7—P1 | 121.5 (3) | C46'—C45—Pd1 | 71.4 (5) |
C12—C7—P1 | 119.0 (3) | C46—C45—Pd1 | 72.7 (4) |
C7—C8—C9 | 119.7 (4) | C46'—C45—H45A | 79.8 |
C7—C8—H8 | 120.2 | C46—C45—H45A | 116.3 |
C9—C8—H8 | 120.2 | Pd1—C45—H45A | 116.3 |
C10—C9—C8 | 120.1 (5) | C46'—C45—H45B | 155.4 |
C10—C9—H9 | 119.9 | C46—C45—H45B | 116.3 |
C8—C9—H9 | 119.9 | Pd1—C45—H45B | 116.3 |
C9—C10—C11 | 120.2 (5) | H45A—C45—H45B | 113.3 |
C9—C10—H10 | 119.9 | C46'—C45—H45C | 116.5 |
C11—C10—H10 | 119.9 | C46—C45—H45C | 154.5 |
C12—C11—C10 | 120.1 (5) | Pd1—C45—H45C | 116.5 |
C12—C11—H11 | 120.0 | H45B—C45—H45C | 82.2 |
C10—C11—H11 | 120.0 | C46'—C45—H45D | 116.5 |
C11—C12—C7 | 120.4 (5) | C46—C45—H45D | 78.9 |
C11—C12—H12 | 119.8 | Pd1—C45—H45D | 116.5 |
C7—C12—H12 | 119.8 | H45A—C45—H45D | 127.3 |
C22—C13—C14 | 119.9 (4) | H45C—C45—H45D | 113.4 |
C22—C13—P1 | 121.4 (3) | C47—C46—C45 | 128.5 (13) |
C14—C13—P1 | 118.4 (3) | C47—C46—Pd1 | 72.2 (5) |
C15—C14—C13 | 121.2 (4) | C45—C46—Pd1 | 71.6 (4) |
C15—C14—H14 | 119.4 | C47—C46—H46A | 113.8 |
C13—C14—H14 | 119.4 | C45—C46—H46A | 113.8 |
C14—C15—C16 | 121.0 (4) | Pd1—C46—H46A | 113.8 |
C14—C15—H15 | 119.5 | C45—C46'—C47 | 132.6 (15) |
C16—C15—H15 | 119.5 | C45—C46'—Pd1 | 73.3 (5) |
C15—C16—C17 | 121.8 (4) | C47—C46'—Pd1 | 73.8 (5) |
C15—C16—C21 | 119.3 (4) | C45—C46'—H46B | 111.7 |
C17—C16—C21 | 118.9 (4) | C47—C46'—H46B | 111.7 |
C18—C17—C16 | 121.0 (4) | Pd1—C46'—H46B | 111.7 |
C18—C17—H17 | 119.5 | C46'—C47—Pd1 | 70.9 (5) |
C16—C17—H17 | 119.5 | C46—C47—Pd1 | 72.3 (5) |
C17—C18—C19 | 120.0 (4) | C46'—C47—H47A | 155.6 |
C17—C18—H18 | 120.0 | C46—C47—H47A | 116.3 |
C19—C18—H18 | 120.0 | Pd1—C47—H47A | 116.3 |
C20—C19—C18 | 120.8 (4) | C46'—C47—H47B | 79.9 |
C20—C19—H19 | 119.6 | C46—C47—H47B | 116.3 |
C18—C19—H19 | 119.6 | Pd1—C47—H47B | 116.3 |
C19—C20—C21 | 120.8 (4) | H47A—C47—H47B | 113.3 |
C19—C20—H20 | 119.6 | C46'—C47—H47C | 116.5 |
C21—C20—H20 | 119.6 | C46—C47—H47C | 78.9 |
C20—C21—C16 | 118.5 (4) | Pd1—C47—H47C | 116.5 |
C20—C21—C22 | 122.2 (3) | H47B—C47—H47C | 127.1 |
C16—C21—C22 | 119.4 (4) | C46'—C47—H47D | 116.5 |
C13—C22—C21 | 119.3 (3) | C46—C47—H47D | 154.6 |
C13—C22—C23 | 123.1 (4) | Pd1—C47—H47D | 116.5 |
C21—C22—C23 | 117.5 (3) | H47A—C47—H47D | 82.2 |
C32—C23—C24 | 119.5 (3) | H47C—C47—H47D | 113.5 |
C32—C23—C22 | 122.4 (3) | O3—S2—O1 | 117.7 (3) |
C24—C23—C22 | 118.1 (3) | O3—S2—O2 | 113.2 (4) |
C29—C24—C25 | 117.1 (4) | O1—S2—O2 | 113.2 (3) |
C29—C24—C23 | 119.9 (4) | O3—S2—C48 | 102.2 (4) |
C25—C24—C23 | 122.9 (3) | O1—S2—C48 | 104.5 (4) |
C26—C25—C24 | 121.2 (4) | O2—S2—C48 | 103.9 (5) |
C26—C25—H25 | 119.4 | F2—C48—F3 | 106.2 (8) |
C24—C25—H25 | 119.4 | F2—C48—F1 | 105.8 (9) |
C25—C26—C27 | 120.3 (4) | F3—C48—F1 | 107.8 (8) |
C25—C26—H26 | 119.9 | F2—C48—S2 | 113.8 (7) |
C27—C26—H26 | 119.9 | F3—C48—S2 | 112.1 (7) |
C28—C27—C26 | 120.6 (4) | F1—C48—S2 | 110.8 (6) |
C28—C27—H27 | 119.7 | Cl1—C49—Cl2 | 113.6 (4) |
C26—C27—H27 | 119.7 | Cl1—C49—H49A | 108.8 |
C27—C28—C29 | 120.7 (4) | Cl2—C49—H49A | 108.8 |
C27—C28—H28 | 119.7 | Cl1—C49—H49B | 108.8 |
C29—C28—H28 | 119.7 | Cl2—C49—H49B | 108.8 |
C28—C29—C30 | 121.7 (4) | H49A—C49—H49B | 107.7 |
C28—C29—C24 | 120.1 (4) | ||
C46'—Pd1—P1—C7 | −84.1 (8) | C27—C28—C29—C24 | 0.6 (7) |
C45—Pd1—P1—C7 | −125.0 (6) | C25—C24—C29—C28 | −1.1 (6) |
C47—Pd1—P1—C7 | −93.8 (2) | C23—C24—C29—C28 | 179.9 (4) |
C46—Pd1—P1—C7 | −116.6 (6) | C25—C24—C29—C30 | 179.3 (4) |
P2—Pd1—P1—C7 | 82.09 (14) | C23—C24—C29—C30 | 0.3 (6) |
C46'—Pd1—P1—C1 | 37.4 (8) | C28—C29—C30—C31 | −179.8 (4) |
C45—Pd1—P1—C1 | −3.5 (6) | C24—C29—C30—C31 | −0.3 (6) |
C47—Pd1—P1—C1 | 27.7 (2) | C29—C30—C31—C32 | 0.2 (6) |
C46—Pd1—P1—C1 | 4.9 (6) | C24—C23—C32—C31 | 0.2 (6) |
P2—Pd1—P1—C1 | −156.38 (14) | C22—C23—C32—C31 | −177.6 (4) |
C46'—Pd1—P1—C13 | 153.6 (8) | C24—C23—C32—P2 | −174.3 (3) |
C45—Pd1—P1—C13 | 112.7 (6) | C22—C23—C32—P2 | 7.9 (5) |
C47—Pd1—P1—C13 | 143.9 (2) | C30—C31—C32—C23 | −0.2 (6) |
C46—Pd1—P1—C13 | 121.1 (6) | C30—C31—C32—P2 | 174.5 (3) |
P2—Pd1—P1—C13 | −40.24 (14) | C39—P2—C32—C23 | −55.7 (4) |
C46'—Pd1—P2—C39 | −107.3 (7) | C38—P2—C32—C23 | −170.3 (3) |
C45—Pd1—P2—C39 | −87.5 (2) | Pd1—P2—C32—C23 | 69.5 (3) |
C47—Pd1—P2—C39 | −109.1 (6) | C39—P2—C32—C31 | 129.7 (3) |
C46—Pd1—P2—C39 | −75.0 (7) | C38—P2—C32—C31 | 15.1 (3) |
P1—Pd1—P2—C39 | 85.36 (14) | Pd1—P2—C32—C31 | −105.1 (3) |
C46'—Pd1—P2—C38 | 17.5 (7) | C38—C33—C34—C35 | −0.9 (7) |
C45—Pd1—P2—C38 | 37.3 (2) | C33—C34—C35—C36 | 1.9 (7) |
C47—Pd1—P2—C38 | 15.7 (6) | C34—C35—C36—C37 | −1.2 (8) |
C46—Pd1—P2—C38 | 49.7 (7) | C35—C36—C37—C38 | −0.6 (7) |
P1—Pd1—P2—C38 | −149.86 (14) | C34—C33—C38—C37 | −0.9 (6) |
C46'—Pd1—P2—C32 | 132.1 (7) | C34—C33—C38—P2 | 177.4 (3) |
C45—Pd1—P2—C32 | 151.8 (2) | C36—C37—C38—C33 | 1.6 (6) |
C47—Pd1—P2—C32 | 130.3 (6) | C36—C37—C38—P2 | −176.5 (3) |
C46—Pd1—P2—C32 | 164.3 (7) | C39—P2—C38—C33 | 159.3 (3) |
P1—Pd1—P2—C32 | −35.27 (14) | C32—P2—C38—C33 | −88.3 (4) |
C7—P1—C1—C6 | −7.2 (4) | Pd1—P2—C38—C33 | 31.8 (4) |
C13—P1—C1—C6 | 105.1 (4) | C39—P2—C38—C37 | −22.5 (4) |
Pd1—P1—C1—C6 | −135.6 (3) | C32—P2—C38—C37 | 89.9 (4) |
C7—P1—C1—C2 | 168.2 (3) | Pd1—P2—C38—C37 | −150.0 (3) |
C13—P1—C1—C2 | −79.5 (4) | C38—P2—C39—C40 | 63.8 (4) |
Pd1—P1—C1—C2 | 39.8 (4) | C32—P2—C39—C40 | −46.2 (4) |
C6—C1—C2—C3 | 0.0 (6) | Pd1—P2—C39—C40 | −170.0 (3) |
P1—C1—C2—C3 | −175.6 (3) | C38—P2—C39—C44 | −118.2 (3) |
C1—C2—C3—C4 | 0.7 (7) | C32—P2—C39—C44 | 131.7 (3) |
C2—C3—C4—C5 | −0.7 (7) | Pd1—P2—C39—C44 | 8.0 (3) |
C3—C4—C5—C6 | 0.1 (7) | C44—C39—C40—C41 | 1.9 (6) |
C2—C1—C6—C5 | −0.7 (6) | P2—C39—C40—C41 | 179.9 (3) |
P1—C1—C6—C5 | 174.7 (3) | C39—C40—C41—C42 | −2.0 (6) |
C4—C5—C6—C1 | 0.6 (7) | C40—C41—C42—C43 | 1.1 (6) |
C1—P1—C7—C8 | 72.6 (4) | C41—C42—C43—C44 | 0.0 (7) |
C13—P1—C7—C8 | −39.1 (4) | C42—C43—C44—C39 | 0.0 (6) |
Pd1—P1—C7—C8 | −163.5 (3) | C40—C39—C44—C43 | −0.9 (6) |
C1—P1—C7—C12 | −107.9 (3) | P2—C39—C44—C43 | −179.0 (3) |
C13—P1—C7—C12 | 140.4 (3) | C47—Pd1—C45—C46' | 20.9 (10) |
Pd1—P1—C7—C12 | 16.0 (4) | C46—Pd1—C45—C46' | 43.4 (6) |
C12—C7—C8—C9 | −0.1 (6) | P2—Pd1—C45—C46' | −152.6 (9) |
P1—C7—C8—C9 | 179.4 (3) | P1—Pd1—C45—C46' | 54.6 (12) |
C7—C8—C9—C10 | 0.6 (7) | C46'—Pd1—C45—C46 | −43.4 (6) |
C8—C9—C10—C11 | −0.4 (7) | C47—Pd1—C45—C46 | −22.5 (9) |
C9—C10—C11—C12 | −0.3 (7) | P2—Pd1—C45—C46 | 164.0 (8) |
C10—C11—C12—C7 | 0.9 (7) | P1—Pd1—C45—C46 | 11.2 (11) |
C8—C7—C12—C11 | −0.7 (6) | C46'—C45—C46—C47 | −33.8 (11) |
P1—C7—C12—C11 | 179.8 (4) | Pd1—C45—C46—C47 | 47.5 (11) |
C7—P1—C13—C22 | −58.5 (4) | C46'—C45—C46—Pd1 | −81.3 (9) |
C1—P1—C13—C22 | −170.5 (3) | C46'—Pd1—C46—C47 | −71.6 (12) |
Pd1—P1—C13—C22 | 70.3 (3) | C45—Pd1—C46—C47 | −142.7 (14) |
C7—P1—C13—C14 | 128.4 (3) | P2—Pd1—C46—C47 | −164.2 (4) |
C1—P1—C13—C14 | 16.4 (4) | P1—Pd1—C46—C47 | 41.2 (11) |
Pd1—P1—C13—C14 | −102.8 (3) | C46'—Pd1—C46—C45 | 71.1 (13) |
C22—C13—C14—C15 | −1.8 (6) | C47—Pd1—C46—C45 | 142.7 (14) |
P1—C13—C14—C15 | 171.4 (4) | P2—Pd1—C46—C45 | −21.5 (11) |
C13—C14—C15—C16 | 0.2 (7) | P1—Pd1—C46—C45 | −176.1 (4) |
C14—C15—C16—C17 | −177.7 (4) | C46—C45—C46'—C47 | 36.9 (13) |
C14—C15—C16—C21 | 1.5 (7) | Pd1—C45—C46'—C47 | −47.8 (14) |
C15—C16—C17—C18 | −179.6 (4) | C46—C45—C46'—Pd1 | 84.7 (9) |
C21—C16—C17—C18 | 1.2 (6) | C47—Pd1—C46'—C45 | −145.4 (16) |
C16—C17—C18—C19 | 0.3 (6) | C46—Pd1—C46'—C45 | −73.0 (14) |
C17—C18—C19—C20 | −0.8 (6) | P2—Pd1—C46'—C45 | 35.5 (12) |
C18—C19—C20—C21 | −0.3 (6) | P1—Pd1—C46'—C45 | −162.2 (3) |
C19—C20—C21—C16 | 1.7 (6) | C45—Pd1—C46'—C47 | 145.4 (16) |
C19—C20—C21—C22 | −178.1 (4) | C46—Pd1—C46'—C47 | 72.4 (12) |
C15—C16—C21—C20 | 178.6 (4) | P2—Pd1—C46'—C47 | −179.1 (5) |
C17—C16—C21—C20 | −2.2 (6) | P1—Pd1—C46'—C47 | −16.8 (14) |
C15—C16—C21—C22 | −1.6 (6) | C45—C46'—C47—C46 | −37.0 (14) |
C17—C16—C21—C22 | 177.6 (4) | Pd1—C46'—C47—C46 | −84.7 (9) |
C14—C13—C22—C21 | 1.6 (6) | C45—C46'—C47—Pd1 | 47.7 (14) |
P1—C13—C22—C21 | −171.3 (3) | C45—C46—C47—C46' | 33.7 (12) |
C14—C13—C22—C23 | −175.7 (4) | Pd1—C46—C47—C46' | 81.0 (9) |
P1—C13—C22—C23 | 11.3 (5) | C45—C46—C47—Pd1 | −47.3 (11) |
C20—C21—C22—C13 | 179.8 (4) | C45—Pd1—C47—C46' | −20.9 (10) |
C16—C21—C22—C13 | 0.0 (6) | C46—Pd1—C47—C46' | −43.5 (6) |
C20—C21—C22—C23 | −2.6 (6) | P2—Pd1—C47—C46' | 2.5 (13) |
C16—C21—C22—C23 | 177.6 (3) | P1—Pd1—C47—C46' | 167.9 (10) |
C13—C22—C23—C32 | −77.0 (5) | C46'—Pd1—C47—C46 | 43.5 (6) |
C21—C22—C23—C32 | 105.6 (4) | C45—Pd1—C47—C46 | 22.6 (9) |
C13—C22—C23—C24 | 105.2 (5) | P2—Pd1—C47—C46 | 45.9 (12) |
C21—C22—C23—C24 | −72.2 (5) | P1—Pd1—C47—C46 | −148.7 (9) |
C32—C23—C24—C29 | −0.3 (6) | O3—S2—C48—F2 | −64.1 (8) |
C22—C23—C24—C29 | 177.6 (4) | O1—S2—C48—F2 | 59.1 (8) |
C32—C23—C24—C25 | −179.3 (4) | O2—S2—C48—F2 | 178.0 (7) |
C22—C23—C24—C25 | −1.4 (6) | O3—S2—C48—F3 | 175.4 (8) |
C29—C24—C25—C26 | 0.7 (6) | O1—S2—C48—F3 | −61.4 (9) |
C23—C24—C25—C26 | 179.6 (4) | O2—S2—C48—F3 | 57.5 (8) |
C24—C25—C26—C27 | 0.4 (7) | O3—S2—C48—F1 | 54.9 (9) |
C25—C26—C27—C28 | −0.9 (8) | O1—S2—C48—F1 | 178.1 (7) |
C26—C27—C28—C29 | 0.5 (8) | O2—S2—C48—F1 | −62.9 (8) |
C27—C28—C29—C30 | −179.9 (4) |
Experimental details
Crystal data | |
Chemical formula | [Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2 |
Mr | 1004.10 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 180 |
a, b, c (Å) | 11.1814 (3), 19.7359 (4), 20.3672 (4) |
V (Å3) | 4494.53 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.70 |
Crystal size (mm) | 0.12 × 0.10 × 0.07 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.898, 0.961 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29207, 7894, 6903 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.075, 1.05 |
No. of reflections | 7894 |
No. of parameters | 560 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.36, −0.42 |
Absolute structure | Flack (1983), 3491 Friedel reflections |
Absolute structure parameter | −0.03 (2) |
Computer programs: COLLECT (Nonius 1998), HKL SCALEPACK (Otwinowski & Minor, 1997), HKL DENZO (Otwinowski & Minor, 1997) and SCALEPACK, SIR92 (Altomare at al., 1994), SHELXTL (Bruker 2001), SHELXTL.
Pd1—C46' | 2.141 (10) | Pd1—C46 | 2.177 (9) |
Pd1—C45 | 2.164 (4) | Pd1—P2 | 2.3000 (11) |
Pd1—C47 | 2.176 (5) | Pd1—P1 | 2.3023 (11) |
C46'—Pd1—C45 | 35.2 (4) | C47—Pd1—P2 | 163.61 (15) |
C46'—Pd1—C47 | 35.3 (3) | C46—Pd1—P2 | 131.9 (3) |
C45—Pd1—C47 | 66.9 (2) | C46'—Pd1—P1 | 134.1 (3) |
C46'—Pd1—C46 | 24.7 (3) | C45—Pd1—P1 | 164.35 (14) |
C45—Pd1—C46 | 35.7 (3) | C47—Pd1—P1 | 99.90 (16) |
C47—Pd1—C46 | 35.4 (3) | C46—Pd1—P1 | 128.9 (3) |
C46'—Pd1—P2 | 128.4 (3) | P2—Pd1—P1 | 95.97 (4) |
C45—Pd1—P2 | 97.97 (14) |
As part of our research devoted to the syntheses and structural characterization of novel chiral catalysts with direct applications in asymmetric hydrogenation processes, we have synthesized the title compound, (I), using a similar experimental procedure to that described for [Pd(C3H5)(C9H18N2)]CF3SO3 (Jones et al., 2003), but using (R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (R-BINAP) as the chiral ligand instead. BINAP, a conformationally flexible atropisometric diphosphine, is a very interesting ligand since, apart from being able to coordinate to several transition metal centres (Ozawa & Hayashi, 1992; Ikariya et al., 1985), it also affords potent catalytic complexes due to the high steric hindrance around the cation. The addition of R-BINAP to the intermediate [Pd(η3-allyl)(thf)2]+ cation displaces the coordinated solvent molecules (THF), forming a seven-membered chelate ring and leading to the formation of [Pd(η3-allyl)(R-BINAP)]+ (Fig. 1). The η3-allyl appears disordered over two different positions with occupancy factors of, approximately, 50% for each. In accordance with what has been observed for related complexes, the Pd metal centre shows a pseudo-square-planar geometry and the Pd—C and Pd—P bond distances are within the expected range of values (see Fig. 1 and Table 1) (Jones et al., 2003; Bruno et al., 2002; Sauthier et al., 2000; Albinati et al., 1991). Individual [Pd(η3-allyl)(R-BINAP)]+ complexes close pack along the b direction, leading to the formation of layers which alternate in an ABAB··· fashion (two layers per b axis repeat) (Fig. 3). Within the layers, small zigzag void spaces are occupied by the trifluoromethanesulfonate anions and dichloromethane molecules (Fig. 3).