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Acta Cryst. (2012). E68, m1574-m1575    [ doi:10.1107/S1600536812048702 ]

[mu]-Carbonato-[kappa]4O,O':O',O''-bis{[2'-(di-tert-butylphosphanyl)biphenyl-2-yl-[kappa]2P,C1]palladium(II)} dichloromethane monosolvate

A. Muller and C. W. Holzapfel

Abstract top

The title compound, [([mu]2-CO3){Pd(P(t-C4H9)2(C12H8)}2]·CH2Cl2, the first CO3-bridged palladium dimer complex reported to date, was obtained while preparing the Pd0 complex with (2-biphenyl)P(tBu)2. In the crystal, each palladium dimer is accompanied by a dichloromethane solvent molecule. Coordination of the carbonate and chelated phosphane ligands gives distorted square-planar environments at the Pd atoms. Important geometrical parameters include Pd-P(av.) = 2.2135 (4) Å, Pd-C(av.) = 1.9648 (16) Å and P-Pd-C = 84.05 (5) and 87.98 (5)°, and O-Pd-O' = 60.56 (4) and 61.13 (4)°. Bonding with the carbonate O atoms shows values of 2.1616 (11) and 2.1452 (11) Å for the Pd-O-Pd bridge, whereas other Pd-O distances are slightly longer at 2.2136 (11) and 2.1946 (11) Å. One of the tert-butyl groups is disordered over two set of sites with an occupancy ratio of 0.723 (6):0.277 (6). Weak C-H...O interactions are observed propagating the molecules along the [100] direction.

Comment top

Zero-valent palladium complexes play a central role as catalysts in organic synthesis. The complexes Pd2(dba)3 or Pd(dba)3, where dba = dibenzylideneacetone, in combination with 2-biphenyl-di-tert-butylphosphane constitutes particularly powerful catalytic systems (Barlenga et al., 2007; Christman et al., 2006; Ohmura et al., 2008). These catalysts were also successfully applied in the hydromethoxycarbonylation of alkenes under conditions previously described (Williams et al., 2008; Omondi et al., 2011). However, the application of these catalysts in the hydromethoxycarbonylation of styrene suggested that dibenzylideneacetone (dba), like other electron deficient alkenes, may have an inhibitory effect, possibly due to its strong co-ordination to Pd0 (de Pater et al., 2005). We therefore removed dba from our catalyst preparation. This resulted in substantial enhancement of reaction rates. The putative catalyst, a complex of Pd0 with (2-biphenyl)P(tBu)2, could not be crystallized. Exposure of the solution to the air resulted in crystals of the title compound, the structure of which was established by single-crystal X-ray diffraction. The formation of the title compound can be rationalized in terms of reaction of the putative complex with oxygen and carbon dioxide.

Molecules of the title compound (Figure 1, Scheme 1) occupy general positions in the P1 space group. The coordination environment for each Pd center is distorted square-planar with P—Pd—C = 84.05/87.98 (5)°, O—Pd—O' = 60.56/61.13 (4)° due to the strained four membered chelation of the carbonato ligand to each metal center. Bonding to the carbonato oxygen atoms shows values of 2.1616 (11)/2.1452 (11) Å for Pd—O—Pd, whereas the Pd—O distances are slightly longer at 2.2136 (11)/2.1946 (11) Å. Weak C—H···O interactions are observed and the resulting packing causes a disorder of one the tertiary butyl groups which was treated appropriately (see the Refinement section for details).

Related literature top

For catalytic studies on palladium complexes [Pd2(dba)3] or [Pd(dba)3)], where dba = dibenzylideneacetone, in combination with 2-biphenyl-di-tert-butylphosphane, see: Barlenga et al. (2007); Christman et al. (2006); Ohmura et al. (2008); Williams et al. (2008); Omondi et al. (2011); de Pater et al. (2005).

Experimental top

To a stirred solution of Pd(dba)2 (574 mg, 1 mmol) in CH2Cl2 (25 ml) at room temperature under argon was added (2-biphenyl)P(tBu)2 (596 mg, 2 mmol). Stirring was continued for 24 hr. During this period the color of the solution changed from dark red to a light orange. The solvent was removed in vacuo and the residue chromatographed over silica (Davisil, 25 g) using gradient elution (0–5% acetone in CH2Cl2). After all of the dba was eluted from the column (150 ml), as indicated by TLC, the remaining absorbed material was eluted using 20% acetone in CH2Cl2 (75 ml). Evaporation of the solvent in vacuo left a colorless amorphous residue (640 mg) which showed a major 31P-NMR signal at -13.5 p.p.m. A solution of the residue in 5:1 cyclohexane-CH2Cl2 was exposed to the atmosphere. As the solvent evaporated, crystals of the title compound were deposited. The colorless crystals (443 mg) were collected after 24 hrs. Good quality crystals (mp. 144–147°C, decomp.) were obtained by exposing a solution of the title compound in CH2Cl2 to vapors of ether.

Refinement top

All methyl and aromatic hydrogen atoms were positioned in geometrically idealized positions with C—H = 0.96 Å and 0.93 Å, respectively. Aromatic hydrogen atoms were allowed to ride on their parent atoms with Uiso(H) = 1.2Ueq, and for methyl hydrogen atoms Uiso(H) = 1.5Ueq was used. The initial positions of methyl hydrogen atoms were located from a Fourier difference map and refined as fixed rotor. Discrepant reflection [001] was removed at the final stages of refinement. A tertiary butyl on P1 showed large thermal ellipsoids and was refined with the methyl groups disordered over two positions. The 1,2 and 1,3 distance restraints (SADI), as well as ellipsoid displacement restraints (SIMU and DELU), were applied to keep refinement stable and reasonable. Occupation parameters of the disordered atoms refined to a 0.72245:0.27755 ratio for parts A and B, respectively. All the above restraints were applied with the default standard deviations. The highest residual peak of 0.56 Å-3 is 0.85 Å from C4 and the deepest hole of -0.48 Å-3 0.81 Å from Pd1, both representing no physical meaning.

Computing details top

Data collection: APEX2 (Bruker, 2011); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT and XPREP (Bruker, 2008); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2005); software used to prepare material for publication: publCIF (Westrip, 2010) and WinGX (Farrugia, 2012).

Figures top
[Figure 1] Fig. 1. View of title compound showing displacement ellipsoids drawn at a 30% probability level and atom-numbering scheme. Secondary component of disordered atoms indicated in cyan. Hydrogen atoms have been omitted for clarity.
µ-Carbonato-κ4O,O':O',O''-bis{[2'-(di- tert-butylphosphanyl)biphenyl-2-yl- κ2P,C1]palladium(II)} dichloromethane monosolvate top
Crystal data top
[Pd2(CO3)(C20H26P)2]·CH2Cl2Z = 2
Mr = 952.49F(000) = 972
Triclinic, P1Dx = 1.543 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.5459 (6) ÅCell parameters from 9940 reflections
b = 14.6579 (11) Åθ = 2.5–28.2°
c = 18.7078 (14) ŵ = 1.12 mm−1
α = 83.866 (2)°T = 100 K
β = 86.457 (2)°Needle, yellow
γ = 86.478 (2)°0.42 × 0.1 × 0.06 mm
V = 2050.3 (3) Å3
Data collection top
Bruker APEX DUO 4K CCD
diffractometer		10165 independent reflections
Graphite monochromator8987 reflections with I > 2σ(I)
Detector resolution: 8.4 pixels mm-1Rint = 0.033
φ and ω scansθmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		h = −10→9
Tmin = 0.650, Tmax = 0.936k = −19→19
86748 measured reflectionsl = −24→24
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.020Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.044H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0104P)2 + 2.0663P]
where P = (Fo2 + 2Fc2)/3
10165 reflections(Δ/σ)max = 0.004
503 parametersΔρmax = 0.56 e Å−3
78 restraintsΔρmin = −0.48 e Å−3
Crystal data top
[Pd2(CO3)(C20H26P)2]·CH2Cl2γ = 86.478 (2)°
Mr = 952.49V = 2050.3 (3) Å3
Triclinic, P1Z = 2
a = 7.5459 (6) ÅMo Kα radiation
b = 14.6579 (11) ŵ = 1.12 mm−1
c = 18.7078 (14) ÅT = 100 K
α = 83.866 (2)°0.42 × 0.1 × 0.06 mm
β = 86.457 (2)°
Data collection top
Bruker APEX DUO 4K CCD
diffractometer		10165 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2008)		8987 reflections with I > 2σ(I)
Tmin = 0.650, Tmax = 0.936Rint = 0.033
86748 measured reflectionsθmax = 28.3°
Refinement top
R[F2 > 2σ(F2)] = 0.020H-atom parameters constrained
wR(F2) = 0.044Δρmax = 0.56 e Å−3
S = 1.03Δρmin = −0.48 e Å−3
10165 reflectionsAbsolute structure: ?
503 parametersFlack parameter: ?
78 restraintsRogers parameter: ?
Special details top

Experimental. The intensity data was collected on a Bruker Apex DUO 4 K CCD diffractometer using an exposure time of 10 s/frame. A total of 4968 frames were collected with a frame width of 0.5° covering up to θ = 28.31° with 99.8% completeness accomplished.

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)
Pd10.883397 (16)0.921980 (7)0.215760 (6)0.01235 (3)
Pd21.238700 (16)0.682903 (8)0.254095 (6)0.01277 (3)
P10.71344 (5)1.04810 (3)0.18774 (2)0.01269 (8)
P21.43043 (6)0.56268 (3)0.26182 (2)0.01438 (8)
C10.8211 (2)0.94764 (11)0.31550 (9)0.0188 (3)
C20.7610 (3)0.87228 (13)0.36043 (10)0.0304 (4)
H20.75040.81570.3410.037*
C30.7167 (4)0.87820 (14)0.43276 (11)0.0423 (6)
H30.6720.82680.46210.051*
C40.7378 (4)0.95913 (15)0.46222 (11)0.0454 (6)
H40.71020.96330.5120.054*
C50.7994 (3)1.03403 (14)0.41859 (10)0.0343 (5)
H50.8161.08910.43920.041*
C60.8381 (2)1.03058 (11)0.34455 (9)0.0200 (3)
C70.8777 (2)1.11743 (11)0.29964 (9)0.0173 (3)
C80.9715 (2)1.18333 (12)0.32779 (10)0.0238 (4)
H81.0161.16990.37440.029*
C91.0016 (3)1.26786 (12)0.28960 (11)0.0269 (4)
H91.06691.31130.30970.032*
C100.9359 (2)1.28830 (11)0.22230 (10)0.0237 (4)
H100.95481.34630.19590.028*
C110.8421 (2)1.22408 (11)0.19310 (9)0.0179 (3)
H110.79651.23910.14690.022*
C120.8134 (2)1.13801 (10)0.23007 (8)0.0147 (3)
C130.4695 (2)1.04852 (11)0.21867 (9)0.0194 (3)
C14A0.4407 (4)1.0692 (3)0.29654 (16)0.0264 (7)0.723 (6)
H14A0.48561.12930.30160.04*0.723 (6)
H14B0.50451.02170.32760.04*0.723 (6)
H14C0.31341.06980.31060.04*0.723 (6)
C15A0.4089 (4)0.9496 (2)0.21425 (19)0.0311 (8)0.723 (6)
H15A0.28240.9470.22920.047*0.723 (6)
H15B0.47840.90570.24610.047*0.723 (6)
H15C0.42780.9340.16460.047*0.723 (6)
C16A0.3543 (4)1.1164 (2)0.17218 (16)0.0284 (8)0.723 (6)
H16A0.35641.09750.12340.043*0.723 (6)
H16B0.40041.17780.17010.043*0.723 (6)
H16C0.23191.11790.1930.043*0.723 (6)
C14B0.4398 (12)1.0218 (7)0.3003 (4)0.032 (2)0.277 (6)
H14D0.50831.06070.32650.047*0.277 (6)
H14E0.47910.95720.3120.047*0.277 (6)
H14F0.31311.03050.31440.047*0.277 (6)
C15B0.3614 (10)0.9902 (6)0.1786 (5)0.033 (2)0.277 (6)
H15D0.24460.9830.20380.05*0.277 (6)
H15E0.42290.92970.17610.05*0.277 (6)
H15F0.34611.020.12980.05*0.277 (6)
C16B0.3913 (10)1.1520 (4)0.2068 (5)0.031 (2)0.277 (6)
H16D0.40651.17470.15570.046*0.277 (6)
H16E0.45481.19020.23540.046*0.277 (6)
H16F0.26461.15470.22180.046*0.277 (6)
C170.7439 (2)1.07393 (11)0.08665 (8)0.0167 (3)
C180.9443 (2)1.08395 (11)0.06970 (8)0.0182 (3)
H18A1.01081.03010.09230.027*
H18B0.98031.13950.08850.027*
H18C0.96951.08870.01750.027*
C190.6405 (3)1.15768 (13)0.04808 (10)0.0272 (4)
H19A0.64631.2110.07510.041*
H19B0.5161.14340.04540.041*
H19C0.69371.1716−0.00070.041*
C200.6905 (2)0.98841 (12)0.05387 (9)0.0227 (4)
H20A0.71690.99590.00170.034*
H20B0.56290.98090.06390.034*
H20C0.75770.93390.07520.034*
C211.2346 (2)0.67858 (12)0.35946 (9)0.0191 (3)
C221.2133 (3)0.76783 (13)0.37983 (10)0.0311 (4)
H221.20430.81830.34370.037*
C231.2050 (4)0.78418 (16)0.45139 (11)0.0432 (6)
H231.18890.84530.46410.052*
C241.2202 (3)0.71151 (17)0.50420 (11)0.0419 (6)
H241.21770.72230.55340.05*
C251.2389 (3)0.62345 (15)0.48512 (10)0.0335 (5)
H251.2490.57370.52190.04*
C261.2437 (2)0.60435 (12)0.41274 (9)0.0218 (4)
C271.2734 (2)0.50673 (12)0.39809 (9)0.0220 (4)
C281.2097 (3)0.43839 (14)0.44993 (11)0.0338 (5)
H281.13230.4560.48870.041*
C291.2561 (3)0.34662 (15)0.44627 (12)0.0395 (5)
H291.20710.30170.48110.047*
C301.3731 (3)0.32008 (13)0.39228 (12)0.0345 (5)
H301.41390.25750.39190.041*
C311.4315 (3)0.38559 (12)0.33809 (10)0.0259 (4)
H311.5110.36690.30030.031*
C321.3757 (2)0.47853 (11)0.33788 (9)0.0187 (3)
C331.6607 (2)0.59679 (11)0.27585 (9)0.0201 (3)
C341.6696 (2)0.61526 (12)0.35490 (10)0.0237 (4)
H34A1.64240.55950.38640.036*
H34B1.58280.66520.36550.036*
H34C1.78930.63280.36310.036*
C351.6989 (3)0.68592 (13)0.22825 (10)0.0273 (4)
H35A1.81340.70730.23960.041*
H35B1.60450.73290.23730.041*
H35C1.70310.67450.17750.041*
C361.8030 (3)0.52133 (14)0.26073 (12)0.0320 (4)
H36A1.80640.51150.20970.048*
H36B1.77450.46420.29020.048*
H36C1.91920.540.27270.048*
C371.4163 (2)0.50734 (11)0.17527 (9)0.0178 (3)
C381.4923 (2)0.57287 (12)0.11282 (9)0.0224 (4)
H38A1.45770.55450.0670.034*
H38B1.62230.57010.11350.034*
H38C1.44550.63580.11810.034*
C391.5068 (3)0.41108 (12)0.16890 (10)0.0250 (4)
H39A1.51130.39780.11860.037*
H39B1.43870.3650.19880.037*
H39C1.6280.40930.18530.037*
C401.2172 (2)0.49930 (11)0.16671 (9)0.0200 (3)
H40A1.15760.56080.1620.03*
H40B1.16570.4630.20910.03*
H40C1.2010.4690.12350.03*
C411.0873 (2)0.79756 (10)0.16155 (8)0.0152 (3)
O11.00361 (16)0.85776 (8)0.12106 (6)0.0185 (2)
O21.06629 (15)0.80314 (7)0.23169 (6)0.0145 (2)
O31.18881 (16)0.73122 (8)0.14164 (6)0.0193 (2)
Cl11.21745 (7)0.30269 (3)0.02618 (3)0.03388 (11)
Cl20.86686 (7)0.39826 (4)0.03411 (3)0.03506 (11)
C421.0296 (3)0.34275 (17)−0.02114 (10)0.0352 (5)
H42A0.97740.2903−0.03990.042*
H42B1.06610.3863−0.06280.042*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.01331 (6)0.00987 (5)0.01393 (5)0.00196 (4)−0.00154 (4)−0.00259 (4)
Pd20.01371 (6)0.01011 (5)0.01427 (6)0.00187 (4)0.00022 (4)−0.00223 (4)
P10.01167 (19)0.01141 (17)0.01529 (18)0.00150 (14)−0.00286 (15)−0.00274 (14)
P20.0119 (2)0.01140 (17)0.01979 (19)0.00081 (15)0.00034 (15)−0.00310 (14)
C10.0232 (9)0.0167 (7)0.0157 (7)0.0048 (6)−0.0005 (6)−0.0015 (6)
C20.0432 (12)0.0189 (8)0.0268 (9)0.0039 (8)0.0068 (8)−0.0001 (7)
C30.0669 (17)0.0276 (10)0.0266 (10)0.0072 (10)0.0140 (10)0.0092 (8)
C40.0765 (19)0.0384 (12)0.0172 (9)0.0134 (12)0.0076 (10)−0.0001 (8)
C50.0571 (15)0.0283 (10)0.0174 (8)0.0074 (9)−0.0028 (9)−0.0077 (7)
C60.0256 (9)0.0194 (8)0.0149 (7)0.0048 (7)−0.0035 (7)−0.0028 (6)
C70.0181 (8)0.0162 (7)0.0184 (7)0.0031 (6)−0.0028 (6)−0.0060 (6)
C80.0245 (9)0.0239 (8)0.0255 (9)0.0045 (7)−0.0097 (7)−0.0125 (7)
C90.0237 (10)0.0200 (8)0.0403 (11)−0.0013 (7)−0.0062 (8)−0.0158 (7)
C100.0218 (9)0.0136 (7)0.0363 (10)−0.0015 (7)−0.0018 (8)−0.0054 (7)
C110.0164 (8)0.0139 (7)0.0233 (8)0.0029 (6)−0.0025 (6)−0.0025 (6)
C120.0127 (8)0.0128 (7)0.0190 (7)0.0016 (6)−0.0008 (6)−0.0056 (6)
C130.0123 (8)0.0199 (8)0.0256 (8)0.0001 (6)−0.0001 (6)−0.0023 (6)
C14A0.0153 (13)0.0355 (18)0.0268 (13)0.0045 (14)0.0042 (10)−0.0028 (13)
C15A0.0212 (15)0.0266 (14)0.0462 (19)−0.0098 (12)0.0047 (13)−0.0055 (13)
C16A0.0167 (13)0.0341 (16)0.0327 (15)0.0069 (11)−0.0026 (11)0.0001 (12)
C14B0.022 (4)0.036 (5)0.033 (4)0.005 (4)0.007 (3)0.004 (4)
C15B0.015 (4)0.038 (5)0.048 (5)−0.011 (3)0.007 (3)−0.011 (4)
C16B0.020 (4)0.024 (3)0.045 (5)0.008 (3)0.011 (3)−0.001 (3)
C170.0154 (8)0.0193 (7)0.0154 (7)0.0034 (6)−0.0042 (6)−0.0021 (6)
C180.0180 (8)0.0210 (8)0.0152 (7)0.0006 (6)−0.0007 (6)−0.0015 (6)
C190.0289 (10)0.0305 (9)0.0210 (8)0.0111 (8)−0.0082 (7)−0.0002 (7)
C200.0209 (9)0.0293 (9)0.0195 (8)0.0010 (7)−0.0077 (7)−0.0085 (7)
C210.0179 (8)0.0228 (8)0.0162 (7)0.0046 (7)0.0000 (6)−0.0046 (6)
C220.0445 (13)0.0269 (9)0.0219 (9)0.0105 (9)−0.0069 (8)−0.0072 (7)
C230.0649 (17)0.0401 (12)0.0258 (10)0.0203 (11)−0.0105 (10)−0.0171 (9)
C240.0516 (15)0.0544 (14)0.0189 (9)0.0192 (11)−0.0043 (9)−0.0116 (9)
C250.0344 (12)0.0438 (12)0.0191 (9)0.0127 (9)−0.0001 (8)0.0024 (8)
C260.0175 (9)0.0265 (9)0.0198 (8)0.0045 (7)0.0023 (7)0.0000 (7)
C270.0176 (9)0.0236 (8)0.0231 (8)0.0006 (7)−0.0025 (7)0.0053 (7)
C280.0289 (11)0.0357 (11)0.0322 (10)0.0004 (9)0.0016 (8)0.0137 (8)
C290.0402 (13)0.0320 (11)0.0428 (12)−0.0078 (9)−0.0076 (10)0.0189 (9)
C300.0414 (13)0.0164 (8)0.0451 (12)−0.0019 (8)−0.0168 (10)0.0080 (8)
C310.0283 (10)0.0178 (8)0.0317 (10)0.0004 (7)−0.0084 (8)−0.0008 (7)
C320.0157 (8)0.0158 (7)0.0241 (8)−0.0007 (6)−0.0055 (6)0.0023 (6)
C330.0128 (8)0.0201 (8)0.0283 (9)−0.0021 (6)0.0004 (7)−0.0070 (7)
C340.0183 (9)0.0240 (8)0.0301 (9)−0.0028 (7)−0.0054 (7)−0.0051 (7)
C350.0255 (10)0.0287 (9)0.0291 (9)−0.0134 (8)0.0035 (8)−0.0050 (7)
C360.0137 (9)0.0330 (10)0.0519 (12)0.0038 (8)−0.0027 (8)−0.0189 (9)
C370.0154 (8)0.0151 (7)0.0236 (8)0.0014 (6)0.0012 (6)−0.0074 (6)
C380.0206 (9)0.0242 (8)0.0225 (8)−0.0003 (7)0.0044 (7)−0.0068 (7)
C390.0241 (10)0.0192 (8)0.0327 (10)0.0056 (7)−0.0022 (8)−0.0117 (7)
C400.0175 (9)0.0181 (8)0.0255 (8)−0.0010 (6)−0.0021 (7)−0.0075 (6)
C410.0162 (8)0.0131 (7)0.0165 (7)−0.0015 (6)−0.0004 (6)−0.0030 (5)
O10.0233 (6)0.0163 (5)0.0156 (5)0.0047 (5)−0.0026 (5)−0.0025 (4)
O20.0179 (6)0.0121 (5)0.0131 (5)0.0029 (4)−0.0002 (4)−0.0021 (4)
O30.0237 (7)0.0160 (5)0.0173 (5)0.0063 (5)0.0002 (5)−0.0033 (4)
Cl10.0317 (3)0.0327 (2)0.0365 (3)0.0012 (2)−0.0078 (2)0.00191 (19)
Cl20.0310 (3)0.0398 (3)0.0311 (2)0.0008 (2)0.0042 (2)0.0063 (2)
C420.0261 (11)0.0578 (14)0.0207 (9)0.0003 (10)−0.0019 (8)−0.0003 (9)
Geometric parameters (Å, º) top
Pd1—C11.9658 (16)C17—C191.549 (2)
Pd1—O22.1616 (11)C18—H18A0.98
Pd1—O12.2136 (11)C18—H18B0.98
Pd1—P12.2185 (4)C18—H18C0.98
Pd1—C412.5650 (15)C19—H19A0.98
Pd2—C211.9638 (16)C19—H19B0.98
Pd2—O22.1452 (11)C19—H19C0.98
Pd2—O32.1946 (11)C20—H20A0.98
Pd2—P22.2085 (4)C20—H20B0.98
Pd2—C412.5522 (16)C20—H20C0.98
P1—C121.8311 (16)C21—C261.396 (2)
P1—C171.8912 (16)C21—C221.398 (2)
P1—C131.8947 (17)C22—C231.382 (3)
P2—C321.8253 (17)C22—H220.95
P2—C331.8789 (18)C23—C241.378 (3)
P2—C371.8983 (17)C23—H230.95
C1—C21.396 (2)C24—C251.372 (3)
C1—C61.400 (2)C24—H240.95
C2—C31.384 (3)C25—C261.410 (3)
C2—H20.95C25—H250.95
C3—C41.382 (3)C26—C271.487 (2)
C3—H30.95C27—C281.403 (2)
C4—C51.383 (3)C27—C321.410 (2)
C4—H40.95C28—C291.377 (3)
C5—C61.403 (2)C28—H280.95
C5—H50.95C29—C301.372 (3)
C6—C71.484 (2)C29—H290.95
C7—C81.397 (2)C30—C311.390 (3)
C7—C121.413 (2)C30—H300.95
C8—C91.387 (3)C31—C321.401 (2)
C8—H80.95C31—H310.95
C9—C101.378 (3)C33—C361.529 (2)
C9—H90.95C33—C351.532 (2)
C10—C111.387 (2)C33—C341.538 (2)
C10—H100.95C34—H34A0.98
C11—C121.395 (2)C34—H34B0.98
C11—H110.95C34—H34C0.98
C13—C15B1.502 (7)C35—H35A0.98
C13—C16A1.519 (3)C35—H35B0.98
C13—C14A1.519 (3)C35—H35C0.98
C13—C14B1.542 (7)C36—H36A0.98
C13—C15A1.559 (3)C36—H36B0.98
C13—C16B1.591 (6)C36—H36C0.98
C14A—H14A0.98C37—C401.534 (2)
C14A—H14B0.98C37—C381.537 (2)
C14A—H14C0.98C37—C391.543 (2)
C15A—H15A0.98C38—H38A0.98
C15A—H15B0.98C38—H38B0.98
C15A—H15C0.98C38—H38C0.98
C16A—H16A0.98C39—H39A0.98
C16A—H16B0.98C39—H39B0.98
C16A—H16C0.98C39—H39C0.98
C14B—H14D0.98C40—H40A0.98
C14B—H14E0.98C40—H40B0.98
C14B—H14F0.98C40—H40C0.98
C15B—H15D0.98C41—O11.2645 (19)
C15B—H15E0.98C41—O31.2735 (18)
C15B—H15F0.98C41—O21.3226 (18)
C16B—H16D0.98Cl1—C421.755 (2)
C16B—H16E0.98Cl2—C421.772 (2)
C16B—H16F0.98C42—H42A0.99
C17—C201.538 (2)C42—H42B0.99
C17—C181.539 (2)
C1—Pd1—O2101.55 (5)H18A—C18—H18B109.5
C1—Pd1—O1162.10 (6)C17—C18—H18C109.5
O2—Pd1—O160.56 (4)H18A—C18—H18C109.5
C1—Pd1—P184.05 (5)H18B—C18—H18C109.5
O2—Pd1—P1173.47 (3)C17—C19—H19A109.5
O1—Pd1—P1113.82 (3)C17—C19—H19B109.5
C1—Pd1—C41132.57 (6)H19A—C19—H19B109.5
O2—Pd1—C4131.03 (4)C17—C19—H19C109.5
O1—Pd1—C4129.53 (4)H19A—C19—H19C109.5
P1—Pd1—C41143.29 (4)H19B—C19—H19C109.5
C21—Pd2—O299.28 (6)C17—C20—H20A109.5
C21—Pd2—O3160.34 (6)C17—C20—H20B109.5
O2—Pd2—O361.13 (4)H20A—C20—H20B109.5
C21—Pd2—P287.98 (5)C17—C20—H20C109.5
O2—Pd2—P2172.20 (3)H20A—C20—H20C109.5
O3—Pd2—P2111.51 (3)H20B—C20—H20C109.5
C21—Pd2—C41130.46 (6)C26—C21—C22119.17 (16)
O2—Pd2—C4131.20 (4)C26—C21—Pd2131.14 (13)
O3—Pd2—C4129.93 (4)C22—C21—Pd2109.66 (12)
P2—Pd2—C41141.39 (4)C23—C22—C21121.45 (18)
C12—P1—C17108.53 (7)C23—C22—H22119.3
C12—P1—C13107.65 (7)C21—C22—H22119.3
C17—P1—C13111.48 (8)C24—C23—C22119.7 (2)
C12—P1—Pd1104.70 (5)C24—C23—H23120.1
C17—P1—Pd1105.77 (5)C22—C23—H23120.1
C13—P1—Pd1118.20 (5)C25—C24—C23119.49 (18)
C32—P2—C33105.51 (8)C25—C24—H24120.3
C32—P2—C37108.66 (8)C23—C24—H24120.3
C33—P2—C37112.96 (8)C24—C25—C26122.14 (18)
C32—P2—Pd2112.67 (6)C24—C25—H25118.9
C33—P2—Pd2111.56 (5)C26—C25—H25118.9
C37—P2—Pd2105.59 (5)C21—C26—C25117.94 (17)
C2—C1—C6119.12 (15)C21—C26—C27124.31 (15)
C2—C1—Pd1114.19 (13)C25—C26—C27117.54 (16)
C6—C1—Pd1126.63 (12)C28—C27—C32117.94 (17)
C3—C2—C1121.38 (18)C28—C27—C26118.37 (17)
C3—C2—H2119.3C32—C27—C26123.44 (15)
C1—C2—H2119.3C29—C28—C27121.9 (2)
C4—C3—C2119.80 (19)C29—C28—H28119
C4—C3—H3120.1C27—C28—H28119
C2—C3—H3120.1C30—C29—C28119.93 (18)
C3—C4—C5119.47 (18)C30—C29—H29120
C3—C4—H4120.3C28—C29—H29120
C5—C4—H4120.3C29—C30—C31119.41 (18)
C4—C5—C6121.59 (19)C29—C30—H30120.3
C4—C5—H5119.2C31—C30—H30120.3
C6—C5—H5119.2C30—C31—C32121.49 (18)
C1—C6—C5118.56 (16)C30—C31—H31119.3
C1—C6—C7122.96 (14)C32—C31—H31119.3
C5—C6—C7118.19 (15)C31—C32—C27118.52 (16)
C8—C7—C12118.55 (15)C31—C32—P2121.72 (14)
C8—C7—C6119.78 (15)C27—C32—P2119.75 (12)
C12—C7—C6121.56 (15)C36—C33—C35110.38 (15)
C9—C8—C7121.81 (17)C36—C33—C34107.79 (15)
C9—C8—H8119.1C35—C33—C34108.05 (14)
C7—C8—H8119.1C36—C33—P2112.38 (12)
C10—C9—C8119.45 (17)C35—C33—P2109.60 (13)
C10—C9—H9120.3C34—C33—P2108.52 (12)
C8—C9—H9120.3C33—C34—H34A109.5
C9—C10—C11119.91 (16)C33—C34—H34B109.5
C9—C10—H10120H34A—C34—H34B109.5
C11—C10—H10120C33—C34—H34C109.5
C10—C11—C12121.51 (16)H34A—C34—H34C109.5
C10—C11—H11119.2H34B—C34—H34C109.5
C12—C11—H11119.2C33—C35—H35A109.5
C11—C12—C7118.75 (15)C33—C35—H35B109.5
C11—C12—P1121.70 (12)H35A—C35—H35B109.5
C7—C12—P1119.31 (12)C33—C35—H35C109.5
C15B—C13—C16A75.0 (4)H35A—C35—H35C109.5
C15B—C13—C14A127.8 (3)H35B—C35—H35C109.5
C16A—C13—C14A108.86 (19)C33—C36—H36A109.5
C15B—C13—C14B109.4 (4)C33—C36—H36B109.5
C16A—C13—C14B126.3 (4)H36A—C36—H36B109.5
C16A—C13—C15A109.0 (2)C33—C36—H36C109.5
C14A—C13—C15A107.6 (2)H36A—C36—H36C109.5
C14B—C13—C15A82.8 (4)H36B—C36—H36C109.5
C15B—C13—C16B108.4 (4)C40—C37—C38109.34 (14)
C14A—C13—C16B80.2 (3)C40—C37—C39106.86 (14)
C14B—C13—C16B104.3 (4)C38—C37—C39107.75 (13)
C15A—C13—C16B138.9 (4)C40—C37—P2105.47 (11)
C15B—C13—P1114.1 (3)C38—C37—P2108.00 (11)
C16A—C13—P1112.88 (14)C39—C37—P2119.15 (12)
C14A—C13—P1111.55 (15)C37—C38—H38A109.5
C14B—C13—P1112.8 (3)C37—C38—H38B109.5
C15A—C13—P1106.77 (14)H38A—C38—H38B109.5
C16B—C13—P1107.2 (3)C37—C38—H38C109.5
C13—C14A—H14A109.5H38A—C38—H38C109.5
C13—C14A—H14B109.5H38B—C38—H38C109.5
C13—C14A—H14C109.5C37—C39—H39A109.5
C13—C15A—H15A109.5C37—C39—H39B109.5
C13—C15A—H15B109.5H39A—C39—H39B109.5
C13—C15A—H15C109.5C37—C39—H39C109.5
C13—C16A—H16A109.5H39A—C39—H39C109.5
C13—C16A—H16B109.5H39B—C39—H39C109.5
C13—C16A—H16C109.5C37—C40—H40A109.5
C13—C14B—H14D109.5C37—C40—H40B109.5
C13—C14B—H14E109.5H40A—C40—H40B109.5
H14D—C14B—H14E109.5C37—C40—H40C109.5
C13—C14B—H14F109.5H40A—C40—H40C109.5
H14D—C14B—H14F109.5H40B—C40—H40C109.5
H14E—C14B—H14F109.5O1—C41—O3126.51 (14)
C13—C15B—H15D109.5O1—C41—O2117.03 (13)
C13—C15B—H15E109.5O3—C41—O2116.45 (14)
H15D—C15B—H15E109.5O1—C41—Pd2174.15 (11)
C13—C15B—H15F109.5O3—C41—Pd259.29 (8)
H15D—C15B—H15F109.5O2—C41—Pd257.16 (7)
H15E—C15B—H15F109.5O1—C41—Pd159.65 (8)
C13—C16B—H16D109.5O3—C41—Pd1173.67 (12)
C13—C16B—H16E109.5O2—C41—Pd157.39 (7)
H16D—C16B—H16E109.5Pd2—C41—Pd1114.53 (6)
C13—C16B—H16F109.5C41—O1—Pd190.82 (9)
H16D—C16B—H16F109.5C41—O2—Pd291.64 (9)
H16E—C16B—H16F109.5C41—O2—Pd191.58 (9)
C20—C17—C18108.11 (13)Pd2—O2—Pd1176.28 (6)
C20—C17—C19106.79 (14)C41—O3—Pd290.78 (9)
C18—C17—C19108.83 (14)Cl1—C42—Cl2111.76 (11)
C20—C17—P1106.62 (11)Cl1—C42—H42A109.3
C18—C17—P1106.29 (11)Cl2—C42—H42A109.3
C19—C17—P1119.73 (11)Cl1—C42—H42B109.3
C17—C18—H18A109.5Cl2—C42—H42B109.3
C17—C18—H18B109.5H42A—C42—H42B107.9
C1—Pd1—P1—C1257.47 (7)C41—Pd2—C21—C22−30.19 (17)
O1—Pd1—P1—C12−121.64 (6)C26—C21—C22—C231.5 (3)
C41—Pd1—P1—C12−119.08 (8)Pd2—C21—C22—C23179.60 (19)
C1—Pd1—P1—C17172.03 (8)C21—C22—C23—C240.8 (4)
O1—Pd1—P1—C17−7.09 (7)C22—C23—C24—C25−1.6 (4)
C41—Pd1—P1—C17−4.52 (9)C23—C24—C25—C260.1 (4)
C1—Pd1—P1—C13−62.29 (8)C22—C21—C26—C25−2.8 (3)
O1—Pd1—P1—C13118.60 (7)Pd2—C21—C26—C25179.48 (15)
C41—Pd1—P1—C13121.16 (9)C22—C21—C26—C27−177.42 (18)
C21—Pd2—P2—C3240.09 (8)Pd2—C21—C26—C274.9 (3)
O3—Pd2—P2—C32−142.55 (7)C24—C25—C26—C212.1 (3)
C41—Pd2—P2—C32−144.76 (8)C24—C25—C26—C27177.1 (2)
C21—Pd2—P2—C33−78.37 (8)C21—C26—C27—C28−154.21 (19)
O3—Pd2—P2—C3398.99 (7)C25—C26—C27—C2831.2 (3)
C41—Pd2—P2—C3396.77 (8)C21—C26—C27—C3231.6 (3)
C21—Pd2—P2—C37158.55 (8)C25—C26—C27—C32−142.96 (19)
O3—Pd2—P2—C37−24.08 (7)C32—C27—C28—C295.3 (3)
C41—Pd2—P2—C37−26.30 (8)C26—C27—C28—C29−169.2 (2)
O2—Pd1—C1—C2−52.97 (15)C27—C28—C29—C302.5 (3)
O1—Pd1—C1—C2−52.2 (3)C28—C29—C30—C31−5.7 (3)
P1—Pd1—C1—C2130.44 (15)C29—C30—C31—C321.0 (3)
C41—Pd1—C1—C2−52.36 (18)C30—C31—C32—C276.7 (3)
O2—Pd1—C1—C6124.33 (16)C30—C31—C32—P2−172.66 (15)
O1—Pd1—C1—C6125.09 (19)C28—C27—C32—C31−9.6 (3)
P1—Pd1—C1—C6−52.27 (16)C26—C27—C32—C31164.54 (17)
C41—Pd1—C1—C6124.93 (15)C28—C27—C32—P2169.78 (15)
C6—C1—C2—C30.6 (3)C26—C27—C32—P2−16.0 (2)
Pd1—C1—C2—C3178.08 (18)C33—P2—C32—C31−83.13 (16)
C1—C2—C3—C4−2.3 (4)C37—P2—C32—C3138.27 (17)
C2—C3—C4—C51.4 (4)Pd2—P2—C32—C31154.91 (14)
C3—C4—C5—C61.3 (4)C33—P2—C32—C2797.47 (15)
C2—C1—C6—C52.0 (3)C37—P2—C32—C27−141.13 (14)
Pd1—C1—C6—C5−175.16 (15)Pd2—P2—C32—C27−24.48 (16)
C2—C1—C6—C7−171.70 (18)C32—P2—C33—C3673.16 (15)
Pd1—C1—C6—C711.1 (3)C37—P2—C33—C36−45.41 (16)
C4—C5—C6—C1−3.0 (3)Pd2—P2—C33—C36−164.17 (12)
C4—C5—C6—C7171.1 (2)C32—P2—C33—C35−163.72 (12)
C1—C6—C7—C8−150.28 (18)C37—P2—C33—C3577.71 (13)
C5—C6—C7—C836.0 (3)Pd2—P2—C33—C35−41.06 (13)
C1—C6—C7—C1233.6 (3)C32—P2—C33—C34−45.94 (13)
C5—C6—C7—C12−140.15 (18)C37—P2—C33—C34−164.51 (11)
C12—C7—C8—C90.5 (3)Pd2—P2—C33—C3476.73 (12)
C6—C7—C8—C9−175.77 (16)C32—P2—C37—C4072.50 (12)
C7—C8—C9—C100.7 (3)C33—P2—C37—C40−170.78 (11)
C8—C9—C10—C11−0.6 (3)Pd2—P2—C37—C40−48.60 (11)
C9—C10—C11—C12−0.6 (3)C32—P2—C37—C38−170.68 (11)
C10—C11—C12—C71.7 (2)C33—P2—C37—C38−53.96 (13)
C10—C11—C12—P1−172.58 (13)Pd2—P2—C37—C3868.22 (12)
C8—C7—C12—C11−1.7 (2)C32—P2—C37—C39−47.43 (15)
C6—C7—C12—C11174.52 (15)C33—P2—C37—C3969.29 (15)
C8—C7—C12—P1172.80 (13)Pd2—P2—C37—C39−168.53 (12)
C6—C7—C12—P1−11.0 (2)C21—Pd2—C41—O3177.75 (10)
C17—P1—C12—C1121.43 (15)O2—Pd2—C41—O3179.84 (15)
C13—P1—C12—C11−99.37 (14)P2—Pd2—C41—O34.13 (13)
Pd1—P1—C12—C11134.03 (12)C21—Pd2—C41—O2−2.09 (13)
C17—P1—C12—C7−152.87 (13)O3—Pd2—C41—O2−179.84 (15)
C13—P1—C12—C786.33 (14)P2—Pd2—C41—O2−175.71 (6)
Pd1—P1—C12—C7−40.27 (13)C21—Pd2—C41—Pd1−3.81 (11)
C12—P1—C13—C15B169.7 (4)O2—Pd2—C41—Pd1−1.73 (6)
C17—P1—C13—C15B50.7 (4)O3—Pd2—C41—Pd1178.44 (14)
Pd1—P1—C13—C15B−72.1 (4)P2—Pd2—C41—Pd1−177.43 (2)
C12—P1—C13—C16A86.48 (18)C1—Pd1—C41—O1179.90 (10)
C17—P1—C13—C16A−32.44 (19)O2—Pd1—C41—O1−178.96 (15)
Pd1—P1—C13—C16A−155.30 (16)P1—Pd1—C41—O1−4.76 (13)
C12—P1—C13—C14A−36.5 (2)C1—Pd1—C41—O2−1.14 (13)
C17—P1—C13—C14A−155.39 (18)O1—Pd1—C41—O2178.96 (15)
Pd1—P1—C13—C14A81.75 (19)P1—Pd1—C41—O2174.19 (6)
C12—P1—C13—C14B−64.6 (4)C1—Pd1—C41—Pd20.58 (11)
C17—P1—C13—C14B176.4 (4)O2—Pd1—C41—Pd21.72 (6)
Pd1—P1—C13—C14B53.6 (4)O1—Pd1—C41—Pd2−179.32 (14)
C12—P1—C13—C15A−153.80 (17)P1—Pd1—C41—Pd2175.92 (2)
C17—P1—C13—C15A87.28 (18)O3—C41—O1—Pd1178.24 (16)
Pd1—P1—C13—C15A−35.58 (18)O2—C41—O1—Pd1−0.99 (14)
C12—P1—C13—C16B49.6 (4)C1—Pd1—O1—C41−0.2 (2)
C17—P1—C13—C16B−69.3 (4)O2—Pd1—O1—C410.62 (9)
Pd1—P1—C13—C16B167.8 (4)P1—Pd1—O1—C41176.89 (9)
C12—P1—C17—C20169.61 (11)O1—C41—O2—Pd2179.15 (13)
C13—P1—C17—C20−71.99 (12)O3—C41—O2—Pd2−0.16 (15)
Pd1—P1—C17—C2057.72 (11)Pd1—C41—O2—Pd2178.14 (6)
C12—P1—C17—C1854.44 (12)O1—C41—O2—Pd11.01 (15)
C13—P1—C17—C18172.84 (10)O3—C41—O2—Pd1−178.29 (13)
Pd1—P1—C17—C18−57.45 (11)Pd2—C41—O2—Pd1−178.14 (6)
C12—P1—C17—C19−69.22 (15)C21—Pd2—O2—C41178.39 (10)
C13—P1—C17—C1949.18 (16)O3—Pd2—O2—C410.09 (9)
Pd1—P1—C17—C19178.90 (13)C1—Pd1—O2—C41179.14 (10)
O2—Pd2—C21—C26146.55 (17)O1—Pd1—O2—C41−0.59 (9)
O3—Pd2—C21—C26150.98 (15)O1—C41—O3—Pd2−179.07 (16)
P2—Pd2—C21—C26−36.33 (17)O2—C41—O3—Pd20.15 (14)
C41—Pd2—C21—C26147.65 (15)C21—Pd2—O3—C41−5.1 (2)
O2—Pd2—C21—C22−31.29 (15)O2—Pd2—O3—C41−0.10 (9)
O3—Pd2—C21—C22−26.9 (3)P2—Pd2—O3—C41−177.23 (9)
P2—Pd2—C21—C22145.83 (14)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C18—H18A···O10.982.533.362 (2)143
C20—H20C···O10.982.273.182 (2)154
C22—H22···O20.952.433.030 (2)121
C35—H35A···O2i0.982.433.358 (2)159
C38—H38C···O30.982.373.223 (2)146
C40—H40A···O30.982.513.377 (2)147
C42—H42A···O3ii0.992.403.190 (2)136
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C18—H18A···O10.982.533.362 (2)142.8
C20—H20C···O10.982.273.182 (2)153.9
C22—H22···O20.952.433.030 (2)120.7
C35—H35A···O2i0.982.433.358 (2)158.6
C38—H38C···O30.982.373.223 (2)145.7
C40—H40A···O30.982.513.377 (2)147.4
C42—H42A···O3ii0.992.403.190 (2)136.1
Symmetry codes: (i) x+1, y, z; (ii) −x+2, −y+1, −z.
Acknowledgements top

Support by the research fund of the University of Johannesburg is gratefully acknowledged.

references
References top

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