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The crystal structure of the title compound, [Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2, has been determined at 180 (2) K in the non-centrosymmetric space group P212121. The structure contains only one crystallographically unique Pd metal centre, exhibiting a pseudo-square-planar geometry, and is formed by cationic layers intercalated by tri­fluoro­methane­sulfonate anions and di­chloro­methane mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803012741/cm6046sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536803012741/cm6046Isup2.hkl
Contains datablock I

CCDC reference: 217427

Key indicators

  • Single-crystal X-ray study
  • T = 180 K
  • Mean [sigma](C-C) = 0.006 Å
  • R factor = 0.041
  • wR factor = 0.075
  • Data-to-parameter ratio = 14.1

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.01 From the CIF: _reflns_number_total 7894 Count of symmetry unique reflns 4421 Completeness (_total/calc) 178.56% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 3473 Fraction of Friedel pairs measured 0.786 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.

Comment top

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).

Experimental top

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).

Refinement top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. A view of the complex cation present in the title compound, showing the labelling scheme for all non-H atoms. Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres. The trifluoromethanesulfonate anion, the dichloromethane molecule and all the atoms of the η3-allyl ligand have been omitted for clarity. Labels for C31, C32, and also for the C7—C12 aromatic ring have been omitted because the atoms are eclipsed.
[Figure 2] Fig. 2. Perspective view along the a direction of (I). Cationic [Pd(η3-allyl)(R-BINAP)]nn+ layers alternate in the b direction in an ABAB··· fashion, and are intercalated by the trifluoromethanesulfonate anions and dichloromethane molecules.
(η3-allyl)[(R)-(+)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl]palladium(II) trifluoromethanesulfonate dichloromethane solvate top
Crystal data top
[Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2F(000) = 2040
Mr = 1004.10Dx = 1.484 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 19214 reflections
a = 11.1814 (3) Åθ = 1.0–25.0°
b = 19.7359 (4) ŵ = 0.70 mm1
c = 20.3672 (4) ÅT = 180 K
V = 4494.53 (18) Å3Block, colourless
Z = 40.12 × 0.10 × 0.07 mm
Data collection top
Nonius KappaCCD
diffractometer
6903 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.064
Thin–slice ω and ϕ scansθmax = 25.0°, θmin = 3.6°
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
h = 1113
Tmin = 0.898, Tmax = 0.961k = 2323
29207 measured reflectionsl = 2424
7894 independent reflections
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.041H-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 reflectionsΔρmax = 0.36 e Å3
560 parametersΔρmin = 0.42 e Å3
0 restraintsAbsolute structure: Flack (1983), 3491 Friedel reflections
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.03 (2)
Crystal data top
[Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2V = 4494.53 (18) Å3
Mr = 1004.10Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 11.1814 (3) ŵ = 0.70 mm1
b = 19.7359 (4) ÅT = 180 K
c = 20.3672 (4) Å0.12 × 0.10 × 0.07 mm
Data collection top
Nonius KappaCCD
diffractometer
7894 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1995)
6903 reflections with I > 2σ(I)
Tmin = 0.898, Tmax = 0.961Rint = 0.064
29207 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.041H-atom parameters constrained
wR(F2) = 0.075Δρmax = 0.36 e Å3
S = 1.05Δρmin = 0.42 e Å3
7894 reflectionsAbsolute structure: Flack (1983), 3491 Friedel reflections
560 parametersAbsolute structure parameter: 0.03 (2)
0 restraints
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Pd10.76466 (3)0.766378 (14)0.109135 (14)0.02748 (8)
P10.81180 (9)0.81691 (5)0.20768 (5)0.0263 (2)
P20.60009 (10)0.70856 (5)0.14722 (5)0.0251 (2)
C10.8986 (4)0.89401 (19)0.1939 (2)0.0273 (9)
C20.8663 (4)0.9358 (2)0.1414 (2)0.0370 (11)
H20.79740.92530.11610.044*
C30.9335 (4)0.9920 (2)0.1260 (2)0.0430 (12)
H30.91031.02030.09050.052*
C41.0335 (4)1.0073 (2)0.1615 (3)0.0435 (13)
H41.08021.04590.15050.052*
C51.0664 (4)0.9669 (2)0.2133 (2)0.0415 (11)
H51.13600.97770.23790.050*
C60.9992 (4)0.9102 (2)0.2301 (2)0.0335 (10)
H61.02220.88280.26620.040*
C70.8965 (3)0.7675 (2)0.2668 (2)0.0303 (9)
C80.9031 (4)0.7863 (2)0.3322 (2)0.0378 (11)
H80.86350.82610.34700.045*
C90.9684 (4)0.7466 (2)0.3763 (2)0.0489 (14)
H90.97250.75910.42130.059*
C101.0265 (5)0.6897 (2)0.3547 (3)0.0561 (15)
H101.07120.66290.38480.067*
C111.0201 (5)0.6710 (2)0.2894 (3)0.0550 (15)
H111.06090.63160.27460.066*
C120.9550 (4)0.7094 (2)0.2458 (2)0.0389 (11)
H120.94990.69600.20110.047*
C130.6753 (4)0.84474 (19)0.25022 (19)0.0259 (9)
C140.6455 (4)0.9147 (2)0.2488 (2)0.0347 (11)
H140.70130.94630.23140.042*
C150.5384 (4)0.9373 (2)0.2718 (2)0.0367 (11)
H150.52050.98430.27020.044*
C160.4543 (4)0.8923 (2)0.2978 (2)0.0305 (10)
C170.3404 (4)0.9146 (2)0.3200 (2)0.0362 (11)
H170.32020.96120.31680.043*
C180.2592 (4)0.8697 (2)0.34579 (19)0.0365 (10)
H180.18320.88540.36020.044*
C190.2883 (4)0.8010 (2)0.35093 (19)0.0353 (10)
H190.23210.77030.36940.042*
C200.3974 (4)0.7773 (2)0.32960 (19)0.0309 (9)
H200.41580.73050.33370.037*
C210.4827 (4)0.82185 (19)0.30170 (19)0.0264 (9)
C220.5958 (4)0.79839 (18)0.27717 (19)0.0234 (9)
C230.6240 (3)0.72433 (18)0.28473 (18)0.0226 (8)
C240.6512 (4)0.69948 (19)0.3492 (2)0.0276 (9)
C250.6551 (4)0.7420 (2)0.40560 (18)0.0350 (10)
H250.63950.78910.40090.042*
C260.6808 (4)0.7164 (2)0.4665 (2)0.0446 (12)
H260.68240.74560.50350.053*
C270.7046 (5)0.6472 (2)0.4743 (2)0.0510 (14)
H270.72360.62990.51660.061*
C280.7010 (4)0.6047 (2)0.4223 (2)0.0422 (12)
H280.71680.55780.42840.051*
C290.6739 (4)0.6293 (2)0.3590 (2)0.0298 (9)
C300.6693 (4)0.5859 (2)0.3039 (2)0.0318 (10)
H300.68460.53890.30950.038*
C310.6438 (4)0.60986 (19)0.2436 (2)0.0269 (10)
H310.64120.57920.20760.032*
C320.6207 (3)0.67951 (19)0.23235 (19)0.0248 (9)
C330.6767 (4)0.5960 (2)0.0793 (2)0.0368 (11)
H330.75340.61580.08520.044*
C340.6670 (5)0.5343 (2)0.0473 (2)0.0457 (12)
H340.73650.51230.03100.055*
C350.5564 (5)0.5049 (2)0.0393 (2)0.0488 (14)
H350.55020.46190.01860.059*
C360.4549 (5)0.5371 (2)0.0610 (2)0.0484 (13)
H360.37870.51680.05450.058*
C370.4639 (4)0.6003 (2)0.0928 (2)0.0360 (11)
H370.39390.62300.10750.043*
C380.5764 (4)0.62941 (19)0.1027 (2)0.0307 (9)
C390.4632 (3)0.7574 (2)0.14657 (18)0.0281 (9)
C400.3583 (4)0.7359 (2)0.1764 (2)0.0371 (10)
H400.35650.69350.19840.045*
C410.2560 (4)0.7757 (3)0.1744 (2)0.0494 (12)
H410.18380.76000.19370.059*
C420.2598 (5)0.8381 (2)0.1441 (2)0.0493 (12)
H420.19020.86570.14340.059*
C430.3623 (4)0.8607 (2)0.1154 (2)0.0437 (11)
H430.36360.90380.09470.052*
C440.4651 (4)0.82081 (19)0.1161 (2)0.0334 (9)
H440.53640.83670.09600.040*
C450.7445 (5)0.7431 (3)0.00591 (19)0.0515 (12)
H45A0.77850.69940.00900.062*0.52 (2)
H45B0.66550.75320.01370.062*0.52 (2)
H45C0.72110.69600.00500.062*0.48 (2)
H45D0.70360.77760.02130.062*0.48 (2)
C460.8204 (12)0.7947 (9)0.0105 (4)0.043 (4)0.52 (2)
H46A0.78660.83880.00490.051*0.52 (2)
C46'0.8574 (13)0.7534 (9)0.0180 (6)0.045 (4)0.48 (2)
H46B0.90410.71020.01720.054*0.48 (2)
C470.9142 (5)0.8012 (3)0.0497 (3)0.0576 (15)
H47A0.94220.84810.05800.069*0.52 (2)
H47B0.98020.76850.04300.069*0.52 (2)
H47C0.90790.84760.03150.069*0.48 (2)
H47D0.99530.78990.06590.069*0.48 (2)
S21.05159 (15)0.56823 (8)0.03748 (8)0.0630 (4)
O11.1652 (4)0.5641 (2)0.0060 (2)0.0815 (13)
O20.9618 (4)0.5271 (3)0.0066 (3)0.1098 (18)
O31.0093 (6)0.6334 (2)0.0557 (3)0.127 (2)
C481.0739 (9)0.5289 (4)0.1150 (5)0.111 (3)
F10.9739 (7)0.5311 (3)0.1509 (3)0.184 (3)
F21.1555 (6)0.5575 (4)0.1504 (3)0.181 (3)
F31.1053 (7)0.4656 (3)0.1093 (3)0.197 (3)
C491.1250 (7)0.4243 (4)0.0829 (5)0.126 (4)
H49A1.13970.47240.07160.151*
H49B1.03850.41550.07730.151*
Cl11.2034 (3)0.37380 (13)0.02904 (14)0.1829 (16)
Cl21.16292 (17)0.41149 (8)0.16415 (12)0.0988 (7)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.02915 (16)0.02861 (14)0.02467 (14)0.00132 (13)0.00557 (14)0.00032 (13)
P10.0251 (6)0.0244 (5)0.0295 (6)0.0023 (4)0.0016 (5)0.0016 (4)
P20.0275 (6)0.0266 (5)0.0212 (5)0.0008 (4)0.0005 (5)0.0017 (4)
C10.024 (2)0.025 (2)0.033 (2)0.0003 (17)0.0055 (19)0.0020 (17)
C20.035 (3)0.033 (2)0.043 (3)0.0001 (19)0.001 (2)0.003 (2)
C30.041 (3)0.034 (2)0.054 (3)0.000 (2)0.015 (2)0.010 (2)
C40.039 (3)0.029 (2)0.063 (4)0.005 (2)0.022 (3)0.001 (2)
C50.035 (3)0.036 (3)0.053 (3)0.005 (2)0.006 (2)0.006 (2)
C60.034 (3)0.031 (2)0.035 (3)0.0030 (19)0.001 (2)0.0032 (18)
C70.022 (2)0.029 (2)0.040 (3)0.006 (2)0.0011 (17)0.005 (2)
C80.033 (3)0.037 (3)0.044 (3)0.0032 (19)0.005 (2)0.004 (2)
C90.039 (3)0.061 (4)0.046 (3)0.010 (2)0.010 (2)0.019 (2)
C100.047 (3)0.038 (3)0.083 (4)0.004 (2)0.020 (3)0.029 (3)
C110.044 (3)0.035 (3)0.086 (5)0.003 (2)0.005 (3)0.012 (3)
C120.037 (3)0.030 (2)0.050 (3)0.0004 (19)0.001 (2)0.005 (2)
C130.026 (2)0.028 (2)0.024 (2)0.0020 (17)0.0007 (18)0.0003 (16)
C140.036 (3)0.026 (2)0.041 (3)0.0056 (19)0.003 (2)0.0007 (19)
C150.044 (3)0.021 (2)0.045 (3)0.002 (2)0.004 (2)0.0019 (19)
C160.031 (2)0.032 (2)0.029 (2)0.0005 (19)0.0044 (19)0.0056 (18)
C170.039 (3)0.038 (3)0.032 (2)0.010 (2)0.003 (2)0.0044 (19)
C180.027 (2)0.052 (3)0.031 (2)0.007 (2)0.004 (2)0.0040 (18)
C190.033 (3)0.046 (3)0.027 (2)0.0052 (19)0.0085 (19)0.0011 (18)
C200.036 (2)0.031 (2)0.026 (2)0.0002 (19)0.0075 (18)0.0007 (18)
C210.032 (2)0.023 (2)0.024 (2)0.0001 (18)0.0003 (18)0.0038 (16)
C220.027 (2)0.023 (2)0.020 (2)0.0028 (17)0.0009 (17)0.0042 (16)
C230.0206 (19)0.023 (2)0.024 (2)0.0014 (16)0.0028 (16)0.0014 (17)
C240.024 (2)0.028 (2)0.031 (2)0.0054 (17)0.0008 (18)0.0013 (18)
C250.037 (2)0.038 (2)0.030 (2)0.003 (2)0.0029 (18)0.0033 (18)
C260.061 (3)0.050 (3)0.023 (2)0.003 (2)0.004 (2)0.0045 (19)
C270.071 (4)0.055 (3)0.027 (3)0.004 (3)0.003 (2)0.013 (2)
C280.052 (3)0.042 (3)0.033 (3)0.005 (2)0.004 (2)0.009 (2)
C290.029 (2)0.029 (2)0.032 (2)0.0001 (18)0.002 (2)0.0045 (18)
C300.030 (2)0.025 (2)0.040 (3)0.0048 (18)0.004 (2)0.0005 (18)
C310.028 (2)0.023 (2)0.029 (2)0.0038 (17)0.0029 (19)0.0012 (17)
C320.022 (2)0.029 (2)0.024 (2)0.0010 (17)0.0035 (17)0.0009 (17)
C330.037 (3)0.043 (3)0.031 (2)0.000 (2)0.005 (2)0.0044 (19)
C340.064 (3)0.040 (3)0.033 (3)0.012 (2)0.001 (2)0.011 (2)
C350.076 (4)0.029 (3)0.042 (3)0.004 (3)0.024 (3)0.014 (2)
C360.056 (3)0.040 (3)0.049 (3)0.009 (2)0.016 (3)0.003 (2)
C370.039 (3)0.031 (2)0.037 (3)0.0012 (19)0.006 (2)0.0001 (19)
C380.041 (2)0.031 (2)0.020 (2)0.0010 (18)0.003 (2)0.0008 (18)
C390.029 (2)0.034 (2)0.021 (2)0.0028 (18)0.0017 (17)0.0066 (17)
C400.035 (2)0.048 (2)0.028 (2)0.002 (2)0.0012 (18)0.004 (2)
C410.031 (3)0.081 (3)0.037 (2)0.009 (3)0.004 (2)0.015 (2)
C420.043 (3)0.063 (3)0.042 (3)0.027 (3)0.010 (3)0.016 (2)
C430.052 (3)0.043 (3)0.036 (3)0.015 (2)0.008 (3)0.004 (2)
C440.043 (3)0.031 (2)0.026 (2)0.0020 (19)0.001 (2)0.0053 (19)
C450.064 (3)0.069 (3)0.021 (2)0.005 (3)0.013 (2)0.0043 (19)
C460.056 (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)
C470.063 (4)0.064 (4)0.047 (3)0.012 (3)0.029 (3)0.007 (3)
S20.0633 (11)0.0567 (9)0.0691 (11)0.0066 (8)0.0052 (8)0.0198 (7)
O10.062 (3)0.098 (3)0.084 (3)0.019 (2)0.015 (2)0.007 (2)
O20.059 (3)0.149 (5)0.122 (4)0.025 (3)0.007 (3)0.008 (4)
O30.196 (6)0.062 (3)0.123 (5)0.045 (3)0.023 (4)0.016 (3)
C480.131 (8)0.104 (6)0.098 (7)0.037 (6)0.011 (7)0.043 (6)
F10.208 (7)0.222 (7)0.122 (4)0.037 (5)0.083 (5)0.088 (4)
F20.166 (6)0.287 (9)0.089 (4)0.042 (6)0.046 (4)0.016 (4)
F30.338 (9)0.106 (4)0.147 (5)0.089 (5)0.028 (6)0.066 (4)
C490.062 (5)0.097 (6)0.220 (11)0.013 (4)0.002 (6)0.067 (6)
Cl10.269 (4)0.1246 (18)0.155 (2)0.112 (2)0.100 (2)0.0565 (16)
Cl20.0806 (13)0.0549 (10)0.161 (2)0.0108 (9)0.0249 (13)0.0050 (10)
Geometric parameters (Å, º) top
Pd1—C46'2.141 (10)C26—C271.401 (6)
Pd1—C452.164 (4)C26—H260.9500
Pd1—C472.176 (5)C27—C281.352 (6)
Pd1—C462.177 (9)C27—H270.9500
Pd1—P22.3000 (11)C28—C291.411 (6)
Pd1—P12.3023 (11)C28—H280.9500
P1—C71.815 (4)C29—C301.411 (6)
P1—C11.827 (4)C30—C311.347 (6)
P1—C131.839 (4)C30—H300.9500
P2—C391.809 (4)C31—C321.417 (5)
P2—C381.825 (4)C31—H310.9500
P2—C321.840 (4)C33—C381.386 (6)
C1—C61.382 (6)C33—C341.386 (6)
C1—C21.398 (6)C33—H330.9500
C2—C31.376 (6)C34—C351.375 (7)
C2—H20.9500C34—H340.9500
C3—C41.366 (7)C35—C361.374 (7)
C3—H30.9500C35—H350.9500
C4—C51.373 (6)C36—C371.410 (6)
C4—H40.9500C36—H360.9500
C5—C61.390 (6)C37—C381.397 (6)
C5—H50.9500C37—H370.9500
C6—H60.9500C39—C401.387 (6)
C7—C81.384 (6)C39—C441.397 (5)
C7—C121.388 (6)C40—C411.388 (6)
C8—C91.398 (6)C40—H400.9500
C8—H80.9500C41—C421.378 (6)
C9—C101.370 (7)C41—H410.9500
C9—H90.9500C42—C431.362 (7)
C10—C111.383 (7)C42—H420.9500
C10—H100.9500C43—C441.394 (6)
C11—C121.376 (6)C43—H430.9500
C11—H110.9500C44—H440.9500
C12—H120.9500C45—C46'1.303 (14)
C13—C221.389 (5)C45—C461.330 (13)
C13—C141.420 (5)C45—H45A0.9900
C14—C151.362 (6)C45—H45B0.9900
C14—H140.9500C45—H45C0.9900
C15—C161.398 (6)C45—H45D0.9900
C15—H150.9500C46—C471.325 (13)
C16—C171.420 (6)C46—H46A1.0000
C16—C211.428 (5)C46'—C471.308 (13)
C17—C181.373 (6)C46'—H46B1.0000
C17—H170.9500C47—H47A0.9900
C18—C191.399 (6)C47—H47B0.9900
C18—H180.9500C47—H47C0.9900
C19—C201.378 (6)C47—H47D0.9900
C19—H190.9500S2—O31.419 (5)
C20—C211.415 (5)S2—O11.425 (4)
C20—H200.9500S2—O21.436 (5)
C21—C221.436 (6)S2—C481.777 (8)
C22—C231.503 (5)C48—F21.293 (11)
C23—C321.386 (5)C48—F31.302 (9)
C23—C241.434 (5)C48—F11.335 (9)
C24—C291.423 (5)C49—Cl11.722 (9)
C24—C251.424 (5)C49—Cl21.727 (9)
C25—C261.370 (6)C49—H49A0.9900
C25—H250.9500C49—H49B0.9900
C46'—Pd1—C4535.2 (4)C30—C29—C24118.2 (4)
C46'—Pd1—C4735.3 (3)C31—C30—C29121.3 (4)
C45—Pd1—C4766.9 (2)C31—C30—H30119.3
C46'—Pd1—C4624.7 (3)C29—C30—H30119.3
C45—Pd1—C4635.7 (3)C30—C31—C32121.7 (4)
C47—Pd1—C4635.4 (3)C30—C31—H31119.1
C46'—Pd1—P2128.4 (3)C32—C31—H31119.1
C45—Pd1—P297.97 (14)C23—C32—C31119.3 (4)
C47—Pd1—P2163.61 (15)C23—C32—P2122.0 (3)
C46—Pd1—P2131.9 (3)C31—C32—P2118.5 (3)
C46'—Pd1—P1134.1 (3)C38—C33—C34121.1 (4)
C45—Pd1—P1164.35 (14)C38—C33—H33119.5
C47—Pd1—P199.90 (16)C34—C33—H33119.5
C46—Pd1—P1128.9 (3)C35—C34—C33119.8 (5)
P2—Pd1—P195.97 (4)C35—C34—H34120.1
C7—P1—C1105.78 (19)C33—C34—H34120.1
C7—P1—C13106.29 (18)C36—C35—C34120.6 (4)
C1—P1—C13105.36 (18)C36—C35—H35119.7
C7—P1—Pd1117.73 (15)C34—C35—H35119.7
C1—P1—Pd1110.38 (14)C35—C36—C37119.9 (5)
C13—P1—Pd1110.50 (13)C35—C36—H36120.1
C39—P2—C38109.24 (18)C37—C36—H36120.1
C39—P2—C32106.18 (18)C38—C37—C36119.6 (4)
C38—P2—C32102.67 (18)C38—C37—H37120.2
C39—P2—Pd1114.22 (13)C36—C37—H37120.2
C38—P2—Pd1111.91 (14)C33—C38—C37118.9 (4)
C32—P2—Pd1111.86 (13)C33—C38—P2117.4 (3)
C6—C1—C2118.8 (4)C37—C38—P2123.6 (3)
C6—C1—P1122.9 (3)C40—C39—C44118.8 (4)
C2—C1—P1118.1 (3)C40—C39—P2123.3 (3)
C3—C2—C1120.5 (4)C44—C39—P2117.9 (3)
C3—C2—H2119.7C39—C40—C41120.7 (4)
C1—C2—H2119.7C39—C40—H40119.6
C4—C3—C2120.3 (4)C41—C40—H40119.6
C4—C3—H3119.8C42—C41—C40119.5 (5)
C2—C3—H3119.8C42—C41—H41120.2
C3—C4—C5119.8 (4)C40—C41—H41120.2
C3—C4—H4120.1C43—C42—C41120.8 (4)
C5—C4—H4120.1C43—C42—H42119.6
C4—C5—C6120.8 (4)C41—C42—H42119.6
C4—C5—H5119.6C42—C43—C44120.3 (4)
C6—C5—H5119.6C42—C43—H43119.9
C1—C6—C5119.7 (4)C44—C43—H43119.9
C1—C6—H6120.1C43—C44—C39119.9 (4)
C5—C6—H6120.1C43—C44—H44120.1
C8—C7—C12119.5 (4)C39—C44—H44120.1
C8—C7—P1121.5 (3)C46'—C45—Pd171.4 (5)
C12—C7—P1119.0 (3)C46—C45—Pd172.7 (4)
C7—C8—C9119.7 (4)C46'—C45—H45A79.8
C7—C8—H8120.2C46—C45—H45A116.3
C9—C8—H8120.2Pd1—C45—H45A116.3
C10—C9—C8120.1 (5)C46'—C45—H45B155.4
C10—C9—H9119.9C46—C45—H45B116.3
C8—C9—H9119.9Pd1—C45—H45B116.3
C9—C10—C11120.2 (5)H45A—C45—H45B113.3
C9—C10—H10119.9C46'—C45—H45C116.5
C11—C10—H10119.9C46—C45—H45C154.5
C12—C11—C10120.1 (5)Pd1—C45—H45C116.5
C12—C11—H11120.0H45B—C45—H45C82.2
C10—C11—H11120.0C46'—C45—H45D116.5
C11—C12—C7120.4 (5)C46—C45—H45D78.9
C11—C12—H12119.8Pd1—C45—H45D116.5
C7—C12—H12119.8H45A—C45—H45D127.3
C22—C13—C14119.9 (4)H45C—C45—H45D113.4
C22—C13—P1121.4 (3)C47—C46—C45128.5 (13)
C14—C13—P1118.4 (3)C47—C46—Pd172.2 (5)
C15—C14—C13121.2 (4)C45—C46—Pd171.6 (4)
C15—C14—H14119.4C47—C46—H46A113.8
C13—C14—H14119.4C45—C46—H46A113.8
C14—C15—C16121.0 (4)Pd1—C46—H46A113.8
C14—C15—H15119.5C45—C46'—C47132.6 (15)
C16—C15—H15119.5C45—C46'—Pd173.3 (5)
C15—C16—C17121.8 (4)C47—C46'—Pd173.8 (5)
C15—C16—C21119.3 (4)C45—C46'—H46B111.7
C17—C16—C21118.9 (4)C47—C46'—H46B111.7
C18—C17—C16121.0 (4)Pd1—C46'—H46B111.7
C18—C17—H17119.5C46'—C47—Pd170.9 (5)
C16—C17—H17119.5C46—C47—Pd172.3 (5)
C17—C18—C19120.0 (4)C46'—C47—H47A155.6
C17—C18—H18120.0C46—C47—H47A116.3
C19—C18—H18120.0Pd1—C47—H47A116.3
C20—C19—C18120.8 (4)C46'—C47—H47B79.9
C20—C19—H19119.6C46—C47—H47B116.3
C18—C19—H19119.6Pd1—C47—H47B116.3
C19—C20—C21120.8 (4)H47A—C47—H47B113.3
C19—C20—H20119.6C46'—C47—H47C116.5
C21—C20—H20119.6C46—C47—H47C78.9
C20—C21—C16118.5 (4)Pd1—C47—H47C116.5
C20—C21—C22122.2 (3)H47B—C47—H47C127.1
C16—C21—C22119.4 (4)C46'—C47—H47D116.5
C13—C22—C21119.3 (3)C46—C47—H47D154.6
C13—C22—C23123.1 (4)Pd1—C47—H47D116.5
C21—C22—C23117.5 (3)H47A—C47—H47D82.2
C32—C23—C24119.5 (3)H47C—C47—H47D113.5
C32—C23—C22122.4 (3)O3—S2—O1117.7 (3)
C24—C23—C22118.1 (3)O3—S2—O2113.2 (4)
C29—C24—C25117.1 (4)O1—S2—O2113.2 (3)
C29—C24—C23119.9 (4)O3—S2—C48102.2 (4)
C25—C24—C23122.9 (3)O1—S2—C48104.5 (4)
C26—C25—C24121.2 (4)O2—S2—C48103.9 (5)
C26—C25—H25119.4F2—C48—F3106.2 (8)
C24—C25—H25119.4F2—C48—F1105.8 (9)
C25—C26—C27120.3 (4)F3—C48—F1107.8 (8)
C25—C26—H26119.9F2—C48—S2113.8 (7)
C27—C26—H26119.9F3—C48—S2112.1 (7)
C28—C27—C26120.6 (4)F1—C48—S2110.8 (6)
C28—C27—H27119.7Cl1—C49—Cl2113.6 (4)
C26—C27—H27119.7Cl1—C49—H49A108.8
C27—C28—C29120.7 (4)Cl2—C49—H49A108.8
C27—C28—H28119.7Cl1—C49—H49B108.8
C29—C28—H28119.7Cl2—C49—H49B108.8
C28—C29—C30121.7 (4)H49A—C49—H49B107.7
C28—C29—C24120.1 (4)
C46'—Pd1—P1—C784.1 (8)C27—C28—C29—C240.6 (7)
C45—Pd1—P1—C7125.0 (6)C25—C24—C29—C281.1 (6)
C47—Pd1—P1—C793.8 (2)C23—C24—C29—C28179.9 (4)
C46—Pd1—P1—C7116.6 (6)C25—C24—C29—C30179.3 (4)
P2—Pd1—P1—C782.09 (14)C23—C24—C29—C300.3 (6)
C46'—Pd1—P1—C137.4 (8)C28—C29—C30—C31179.8 (4)
C45—Pd1—P1—C13.5 (6)C24—C29—C30—C310.3 (6)
C47—Pd1—P1—C127.7 (2)C29—C30—C31—C320.2 (6)
C46—Pd1—P1—C14.9 (6)C24—C23—C32—C310.2 (6)
P2—Pd1—P1—C1156.38 (14)C22—C23—C32—C31177.6 (4)
C46'—Pd1—P1—C13153.6 (8)C24—C23—C32—P2174.3 (3)
C45—Pd1—P1—C13112.7 (6)C22—C23—C32—P27.9 (5)
C47—Pd1—P1—C13143.9 (2)C30—C31—C32—C230.2 (6)
C46—Pd1—P1—C13121.1 (6)C30—C31—C32—P2174.5 (3)
P2—Pd1—P1—C1340.24 (14)C39—P2—C32—C2355.7 (4)
C46'—Pd1—P2—C39107.3 (7)C38—P2—C32—C23170.3 (3)
C45—Pd1—P2—C3987.5 (2)Pd1—P2—C32—C2369.5 (3)
C47—Pd1—P2—C39109.1 (6)C39—P2—C32—C31129.7 (3)
C46—Pd1—P2—C3975.0 (7)C38—P2—C32—C3115.1 (3)
P1—Pd1—P2—C3985.36 (14)Pd1—P2—C32—C31105.1 (3)
C46'—Pd1—P2—C3817.5 (7)C38—C33—C34—C350.9 (7)
C45—Pd1—P2—C3837.3 (2)C33—C34—C35—C361.9 (7)
C47—Pd1—P2—C3815.7 (6)C34—C35—C36—C371.2 (8)
C46—Pd1—P2—C3849.7 (7)C35—C36—C37—C380.6 (7)
P1—Pd1—P2—C38149.86 (14)C34—C33—C38—C370.9 (6)
C46'—Pd1—P2—C32132.1 (7)C34—C33—C38—P2177.4 (3)
C45—Pd1—P2—C32151.8 (2)C36—C37—C38—C331.6 (6)
C47—Pd1—P2—C32130.3 (6)C36—C37—C38—P2176.5 (3)
C46—Pd1—P2—C32164.3 (7)C39—P2—C38—C33159.3 (3)
P1—Pd1—P2—C3235.27 (14)C32—P2—C38—C3388.3 (4)
C7—P1—C1—C67.2 (4)Pd1—P2—C38—C3331.8 (4)
C13—P1—C1—C6105.1 (4)C39—P2—C38—C3722.5 (4)
Pd1—P1—C1—C6135.6 (3)C32—P2—C38—C3789.9 (4)
C7—P1—C1—C2168.2 (3)Pd1—P2—C38—C37150.0 (3)
C13—P1—C1—C279.5 (4)C38—P2—C39—C4063.8 (4)
Pd1—P1—C1—C239.8 (4)C32—P2—C39—C4046.2 (4)
C6—C1—C2—C30.0 (6)Pd1—P2—C39—C40170.0 (3)
P1—C1—C2—C3175.6 (3)C38—P2—C39—C44118.2 (3)
C1—C2—C3—C40.7 (7)C32—P2—C39—C44131.7 (3)
C2—C3—C4—C50.7 (7)Pd1—P2—C39—C448.0 (3)
C3—C4—C5—C60.1 (7)C44—C39—C40—C411.9 (6)
C2—C1—C6—C50.7 (6)P2—C39—C40—C41179.9 (3)
P1—C1—C6—C5174.7 (3)C39—C40—C41—C422.0 (6)
C4—C5—C6—C10.6 (7)C40—C41—C42—C431.1 (6)
C1—P1—C7—C872.6 (4)C41—C42—C43—C440.0 (7)
C13—P1—C7—C839.1 (4)C42—C43—C44—C390.0 (6)
Pd1—P1—C7—C8163.5 (3)C40—C39—C44—C430.9 (6)
C1—P1—C7—C12107.9 (3)P2—C39—C44—C43179.0 (3)
C13—P1—C7—C12140.4 (3)C47—Pd1—C45—C46'20.9 (10)
Pd1—P1—C7—C1216.0 (4)C46—Pd1—C45—C46'43.4 (6)
C12—C7—C8—C90.1 (6)P2—Pd1—C45—C46'152.6 (9)
P1—C7—C8—C9179.4 (3)P1—Pd1—C45—C46'54.6 (12)
C7—C8—C9—C100.6 (7)C46'—Pd1—C45—C4643.4 (6)
C8—C9—C10—C110.4 (7)C47—Pd1—C45—C4622.5 (9)
C9—C10—C11—C120.3 (7)P2—Pd1—C45—C46164.0 (8)
C10—C11—C12—C70.9 (7)P1—Pd1—C45—C4611.2 (11)
C8—C7—C12—C110.7 (6)C46'—C45—C46—C4733.8 (11)
P1—C7—C12—C11179.8 (4)Pd1—C45—C46—C4747.5 (11)
C7—P1—C13—C2258.5 (4)C46'—C45—C46—Pd181.3 (9)
C1—P1—C13—C22170.5 (3)C46'—Pd1—C46—C4771.6 (12)
Pd1—P1—C13—C2270.3 (3)C45—Pd1—C46—C47142.7 (14)
C7—P1—C13—C14128.4 (3)P2—Pd1—C46—C47164.2 (4)
C1—P1—C13—C1416.4 (4)P1—Pd1—C46—C4741.2 (11)
Pd1—P1—C13—C14102.8 (3)C46'—Pd1—C46—C4571.1 (13)
C22—C13—C14—C151.8 (6)C47—Pd1—C46—C45142.7 (14)
P1—C13—C14—C15171.4 (4)P2—Pd1—C46—C4521.5 (11)
C13—C14—C15—C160.2 (7)P1—Pd1—C46—C45176.1 (4)
C14—C15—C16—C17177.7 (4)C46—C45—C46'—C4736.9 (13)
C14—C15—C16—C211.5 (7)Pd1—C45—C46'—C4747.8 (14)
C15—C16—C17—C18179.6 (4)C46—C45—C46'—Pd184.7 (9)
C21—C16—C17—C181.2 (6)C47—Pd1—C46'—C45145.4 (16)
C16—C17—C18—C190.3 (6)C46—Pd1—C46'—C4573.0 (14)
C17—C18—C19—C200.8 (6)P2—Pd1—C46'—C4535.5 (12)
C18—C19—C20—C210.3 (6)P1—Pd1—C46'—C45162.2 (3)
C19—C20—C21—C161.7 (6)C45—Pd1—C46'—C47145.4 (16)
C19—C20—C21—C22178.1 (4)C46—Pd1—C46'—C4772.4 (12)
C15—C16—C21—C20178.6 (4)P2—Pd1—C46'—C47179.1 (5)
C17—C16—C21—C202.2 (6)P1—Pd1—C46'—C4716.8 (14)
C15—C16—C21—C221.6 (6)C45—C46'—C47—C4637.0 (14)
C17—C16—C21—C22177.6 (4)Pd1—C46'—C47—C4684.7 (9)
C14—C13—C22—C211.6 (6)C45—C46'—C47—Pd147.7 (14)
P1—C13—C22—C21171.3 (3)C45—C46—C47—C46'33.7 (12)
C14—C13—C22—C23175.7 (4)Pd1—C46—C47—C46'81.0 (9)
P1—C13—C22—C2311.3 (5)C45—C46—C47—Pd147.3 (11)
C20—C21—C22—C13179.8 (4)C45—Pd1—C47—C46'20.9 (10)
C16—C21—C22—C130.0 (6)C46—Pd1—C47—C46'43.5 (6)
C20—C21—C22—C232.6 (6)P2—Pd1—C47—C46'2.5 (13)
C16—C21—C22—C23177.6 (3)P1—Pd1—C47—C46'167.9 (10)
C13—C22—C23—C3277.0 (5)C46'—Pd1—C47—C4643.5 (6)
C21—C22—C23—C32105.6 (4)C45—Pd1—C47—C4622.6 (9)
C13—C22—C23—C24105.2 (5)P2—Pd1—C47—C4645.9 (12)
C21—C22—C23—C2472.2 (5)P1—Pd1—C47—C46148.7 (9)
C32—C23—C24—C290.3 (6)O3—S2—C48—F264.1 (8)
C22—C23—C24—C29177.6 (4)O1—S2—C48—F259.1 (8)
C32—C23—C24—C25179.3 (4)O2—S2—C48—F2178.0 (7)
C22—C23—C24—C251.4 (6)O3—S2—C48—F3175.4 (8)
C29—C24—C25—C260.7 (6)O1—S2—C48—F361.4 (9)
C23—C24—C25—C26179.6 (4)O2—S2—C48—F357.5 (8)
C24—C25—C26—C270.4 (7)O3—S2—C48—F154.9 (9)
C25—C26—C27—C280.9 (8)O1—S2—C48—F1178.1 (7)
C26—C27—C28—C290.5 (8)O2—S2—C48—F162.9 (8)
C27—C28—C29—C30179.9 (4)

Experimental details

Crystal data
Chemical formula[Pd(C3H5)(C44H32P2)](CF3SO3)·CH2Cl2
Mr1004.10
Crystal system, space groupOrthorhombic, P212121
Temperature (K)180
a, b, c (Å)11.1814 (3), 19.7359 (4), 20.3672 (4)
V3)4494.53 (18)
Z4
Radiation typeMo Kα
µ (mm1)0.70
Crystal size (mm)0.12 × 0.10 × 0.07
Data collection
DiffractometerNonius KappaCCD
diffractometer
Absorption correctionMulti-scan
(SORTAV; Blessing, 1995)
Tmin, Tmax0.898, 0.961
No. of measured, independent and
observed [I > 2σ(I)] reflections
29207, 7894, 6903
Rint0.064
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.041, 0.075, 1.05
No. of reflections7894
No. of parameters560
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.36, 0.42
Absolute structureFlack (1983), 3491 Friedel reflections
Absolute structure parameter0.03 (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.

Selected geometric parameters (Å, º) top
Pd1—C46'2.141 (10)Pd1—C462.177 (9)
Pd1—C452.164 (4)Pd1—P22.3000 (11)
Pd1—C472.176 (5)Pd1—P12.3023 (11)
C46'—Pd1—C4535.2 (4)C47—Pd1—P2163.61 (15)
C46'—Pd1—C4735.3 (3)C46—Pd1—P2131.9 (3)
C45—Pd1—C4766.9 (2)C46'—Pd1—P1134.1 (3)
C46'—Pd1—C4624.7 (3)C45—Pd1—P1164.35 (14)
C45—Pd1—C4635.7 (3)C47—Pd1—P199.90 (16)
C47—Pd1—C4635.4 (3)C46—Pd1—P1128.9 (3)
C46'—Pd1—P2128.4 (3)P2—Pd1—P195.97 (4)
C45—Pd1—P297.97 (14)
 

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