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Acta Crystallogr Sect E Struct Rep Online. 2009 August 1; 65(Pt 8): m940.
Published online 2009 July 18. doi:  10.1107/S1600536809027408
PMCID: PMC2977421

trans-Dibromidobis(triphenyl­phosphine-κP)palladium(II) chloro­form monosolvate

Abstract

The PdII atom in the title compound, [PdBr2{P(C6H5)3}2]·CHCl3, lies on a twofold rotation axis and is coordinated in a distorted square-planar geometry by two P atoms from two triphenyl­phosphine ligands and by two Br atoms in a trans arrangement. The chloro­form solvent mol­ecule is equally disordered about another twofold rotation axis.

Related literature

For isostructural PdI2(PPh3)2·CHCl3, see: Kubota et al. (1991 [triangle]). For the other solvates of PdBr2(PPh3)2, see: Crawforth et al. (2005 [triangle]); Rodríguez et al. (2007 [triangle]); Stark & Whitmire (1997 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0m940-scheme1.jpg

Experimental

Crystal data

  • [PdBr2(C18H15P)2]·CHCl3
  • M r = 910.13
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0m940-efi1.jpg
  • a = 12.2314 (2) Å
  • b = 14.4754 (2) Å
  • c = 20.1653 (3) Å
  • β = 92.477 (1)°
  • V = 3567.02 (9) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 3.10 mm−1
  • T = 153 K
  • 0.30 × 0.25 × 0.20 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.456, T max = 0.576 (expected range = 0.426–0.538)
  • 16862 measured reflections
  • 4110 independent reflections
  • 3266 reflections with I > 2σ(I)
  • R int = 0.018

Refinement

  • R[F 2 > 2σ(F 2)] = 0.023
  • wR(F 2) = 0.061
  • S = 1.02
  • 4110 reflections
  • 222 parameters
  • 24 restraints
  • H-atom parameters constrained
  • Δρmax = 0.47 e Å−3
  • Δρmin = −0.36 e Å−3

Data collection: APEX2 (Bruker, 2007 [triangle]); cell refinement: SAINT (Bruker, 2007 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Selected bond lengths (Å)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809027408/hy2209sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027408/hy2209Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the University of Malaya (RG020/09AFR) for supporting this study.

supplementary crystallographic information

Experimental

Commercially available dark-brown bis(triphenylphosphine)palladium dichloride (0.70 g, 1 mmol) and 4-dimethylaminopyridinium hydrobromide perbromide (0.36 g, 1 mmol) were heated in an ethanol/chloroform mixture (1:1 v/v, 100 ml) for an hour. The solution was filtered and a small amount of deep yellow crystals were isolated along with some dark brown material.

Refinement

H atoms were placed at calculated positions (C–H = 0.95 and 1.00 Å) and treated as riding on their parent atoms, with Uiso(H) = 1.2Ueq(C). The chloroform molecule is disordered about a twofold rotation axis, and was allowed to refine off the symmetry element as a whole molecule of 0.5 site occupancy. The three C—Cl distances were restrained to within 0.01 Å of each other, as were the Cl···Cl distances. The anisotropic displacements of the Cl atoms were restrained to be nearly isotropic.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 70% probability level.

Crystal data

[PdBr2(C18H15P)2]·CHCl3F(000) = 1800
Mr = 910.13Dx = 1.695 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 6987 reflections
a = 12.2314 (2) Åθ = 2.4–28.3°
b = 14.4754 (2) ŵ = 3.10 mm1
c = 20.1653 (3) ÅT = 153 K
β = 92.477 (1)°Prism, brown
V = 3567.02 (9) Å30.30 × 0.25 × 0.20 mm
Z = 4

Data collection

Bruker SMART APEX CCD diffractometer4110 independent reflections
Radiation source: fine-focus sealed tube3266 reflections with I > 2σ(I)
graphiteRint = 0.018
[var phi] and ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −15→15
Tmin = 0.456, Tmax = 0.576k = −18→18
16862 measured reflectionsl = −26→26

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.023Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.061H-atom parameters constrained
S = 1.02w = 1/[σ2(Fo2) + (0.0263P)2 + 6.7144P] where P = (Fo2 + 2Fc2)/3
4110 reflections(Δ/σ)max = 0.001
222 parametersΔρmax = 0.47 e Å3
24 restraintsΔρmin = −0.36 e Å3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/UeqOcc. (<1)
Pd10.50000.250839 (14)0.25000.01811 (6)
Br10.322982 (17)0.253392 (15)0.299982 (11)0.02692 (7)
P10.59326 (4)0.25342 (3)0.35355 (3)0.01868 (11)
C10.70341 (17)0.16892 (14)0.35728 (10)0.0226 (4)
C20.6778 (2)0.08037 (16)0.33385 (12)0.0324 (5)
H20.60640.06750.31590.039*
C30.7560 (2)0.01137 (17)0.33665 (13)0.0418 (6)
H30.7378−0.04920.32170.050*
C40.8602 (2)0.0307 (2)0.36119 (13)0.0465 (7)
H40.9142−0.01650.36240.056*
C50.8869 (2)0.1177 (2)0.38400 (14)0.0443 (7)
H50.95910.13030.40080.053*
C60.80823 (19)0.18742 (17)0.38251 (11)0.0306 (5)
H60.82640.24730.39870.037*
C70.51852 (17)0.22807 (14)0.42793 (10)0.0218 (4)
C80.4458 (2)0.29338 (17)0.45150 (12)0.0339 (5)
H80.43570.35040.42870.041*
C90.3886 (2)0.2759 (2)0.50751 (13)0.0405 (6)
H90.33970.32120.52310.049*
C100.4014 (2)0.19368 (19)0.54117 (12)0.0369 (6)
H100.36130.18200.57960.044*
C110.4724 (2)0.12875 (17)0.51881 (12)0.0356 (6)
H110.48210.07210.54210.043*
C120.53046 (19)0.14535 (15)0.46205 (11)0.0292 (5)
H120.57870.09950.44660.035*
C130.65111 (17)0.36690 (14)0.37174 (10)0.0219 (4)
C140.6954 (2)0.38791 (16)0.43498 (11)0.0314 (5)
H140.69380.34320.46940.038*
C150.7417 (2)0.47408 (16)0.44744 (12)0.0352 (6)
H150.77200.48810.49040.042*
C160.7439 (2)0.53955 (15)0.39760 (12)0.0316 (5)
H160.77760.59780.40600.038*
C170.6973 (2)0.52028 (15)0.33583 (12)0.0315 (5)
H170.69680.56600.30200.038*
C180.65112 (18)0.43408 (14)0.32274 (11)0.0258 (5)
H180.61930.42110.27990.031*
Cl10.0544 (6)0.4068 (4)0.1875 (3)0.083 (2)0.50
Cl2−0.0249 (2)0.23500 (12)0.23506 (13)0.0769 (8)0.50
Cl3−0.0654 (5)0.4028 (2)0.3067 (2)0.0454 (8)0.50
C190.0330 (4)0.3413 (3)0.2596 (2)0.0423 (13)0.50
H190.10300.33210.28620.051*0.50

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pd10.02113 (11)0.01538 (10)0.01773 (11)0.000−0.00004 (8)0.000
Br10.02633 (11)0.02758 (12)0.02707 (12)−0.00200 (9)0.00362 (8)0.00051 (9)
P10.0216 (2)0.0161 (2)0.0182 (2)0.0013 (2)−0.00033 (19)0.00040 (19)
C10.0282 (11)0.0208 (10)0.0190 (10)0.0061 (8)0.0032 (8)0.0033 (8)
C20.0430 (14)0.0238 (11)0.0302 (12)0.0056 (10)0.0000 (10)−0.0027 (9)
C30.0663 (19)0.0268 (12)0.0327 (13)0.0174 (12)0.0091 (13)0.0022 (10)
C40.0561 (18)0.0461 (16)0.0382 (15)0.0334 (14)0.0129 (13)0.0146 (12)
C50.0313 (13)0.0581 (18)0.0434 (15)0.0148 (12)0.0005 (11)0.0121 (13)
C60.0291 (12)0.0335 (12)0.0292 (12)0.0037 (9)0.0019 (10)0.0050 (9)
C70.0223 (10)0.0233 (10)0.0194 (10)−0.0015 (8)−0.0020 (8)0.0006 (8)
C80.0394 (13)0.0319 (13)0.0311 (13)0.0094 (11)0.0082 (11)0.0063 (10)
C90.0385 (14)0.0485 (15)0.0353 (14)0.0093 (12)0.0113 (11)−0.0042 (12)
C100.0363 (13)0.0515 (16)0.0234 (12)−0.0087 (12)0.0078 (10)0.0012 (11)
C110.0462 (15)0.0323 (13)0.0286 (12)−0.0070 (11)0.0047 (11)0.0071 (10)
C120.0361 (13)0.0232 (11)0.0284 (12)0.0003 (9)0.0031 (10)0.0021 (9)
C130.0247 (10)0.0178 (9)0.0232 (10)0.0005 (8)0.0011 (8)−0.0023 (8)
C140.0429 (14)0.0257 (11)0.0253 (11)−0.0031 (10)−0.0036 (10)0.0004 (9)
C150.0459 (14)0.0312 (12)0.0279 (12)−0.0034 (11)−0.0060 (11)−0.0074 (10)
C160.0375 (13)0.0212 (11)0.0366 (13)−0.0056 (10)0.0062 (10)−0.0084 (9)
C170.0429 (14)0.0206 (10)0.0315 (12)−0.0019 (10)0.0077 (11)0.0018 (9)
C180.0329 (12)0.0210 (10)0.0233 (11)0.0002 (9)0.0012 (9)−0.0008 (8)
Cl10.087 (3)0.103 (3)0.059 (2)0.013 (2)0.0104 (18)0.0265 (19)
Cl20.078 (2)0.0667 (10)0.089 (2)−0.0211 (10)0.0363 (14)−0.0134 (10)
Cl30.0476 (13)0.0525 (16)0.0375 (14)0.0017 (12)0.0166 (12)−0.0003 (12)
C190.030 (3)0.056 (3)0.041 (3)0.004 (2)−0.003 (2)0.007 (3)

Geometric parameters (Å, °)

Pd1—P12.3360 (5)C9—C101.376 (4)
Pd1—P1i2.3360 (5)C9—H90.9500
Pd1—Br12.4277 (2)C10—C111.369 (4)
Pd1—Br1i2.4277 (2)C10—H100.9500
P1—C11.819 (2)C11—C121.394 (3)
P1—C131.820 (2)C11—H110.9500
P1—C71.827 (2)C12—H120.9500
C1—C61.385 (3)C13—C181.386 (3)
C1—C21.397 (3)C13—C141.397 (3)
C2—C31.382 (3)C14—C151.388 (3)
C2—H20.9500C14—H140.9500
C3—C41.377 (4)C15—C161.383 (3)
C3—H30.9500C15—H150.9500
C4—C51.375 (4)C16—C171.376 (3)
C4—H40.9500C16—H160.9500
C5—C61.394 (3)C17—C181.390 (3)
C5—H50.9500C17—H170.9500
C6—H60.9500C18—H180.9500
C7—C121.386 (3)Cl1—C191.764 (5)
C7—C81.395 (3)Cl2—C191.756 (4)
C8—C91.377 (3)Cl3—C191.800 (5)
C8—H80.9500C19—H191.0000
P1—Pd1—P1i178.16 (3)C10—C9—C8120.8 (2)
P1—Pd1—Br192.204 (14)C10—C9—H9119.6
P1i—Pd1—Br187.768 (14)C8—C9—H9119.6
P1—Pd1—Br1i87.768 (14)C11—C10—C9119.5 (2)
P1i—Pd1—Br1i92.204 (14)C11—C10—H10120.3
Br1—Pd1—Br1i178.256 (14)C9—C10—H10120.3
C1—P1—C13108.54 (10)C10—C11—C12120.3 (2)
C1—P1—C7103.12 (9)C10—C11—H11119.8
C13—P1—C7102.70 (9)C12—C11—H11119.8
C1—P1—Pd1111.00 (7)C7—C12—C11120.7 (2)
C13—P1—Pd1111.42 (7)C7—C12—H12119.7
C7—P1—Pd1119.22 (7)C11—C12—H12119.7
C6—C1—C2119.5 (2)C18—C13—C14119.07 (19)
C6—C1—P1123.88 (17)C18—C13—P1120.10 (16)
C2—C1—P1116.65 (17)C14—C13—P1120.83 (16)
C3—C2—C1120.4 (2)C15—C14—C13120.0 (2)
C3—C2—H2119.8C15—C14—H14120.0
C1—C2—H2119.8C13—C14—H14120.0
C4—C3—C2119.7 (2)C16—C15—C14120.3 (2)
C4—C3—H3120.1C16—C15—H15119.8
C2—C3—H3120.1C14—C15—H15119.8
C5—C4—C3120.6 (2)C17—C16—C15119.9 (2)
C5—C4—H4119.7C17—C16—H16120.0
C3—C4—H4119.7C15—C16—H16120.0
C4—C5—C6120.2 (3)C16—C17—C18120.2 (2)
C4—C5—H5119.9C16—C17—H17119.9
C6—C5—H5119.9C18—C17—H17119.9
C1—C6—C5119.7 (2)C13—C18—C17120.4 (2)
C1—C6—H6120.2C13—C18—H18119.8
C5—C6—H6120.2C17—C18—H18119.8
C12—C7—C8118.1 (2)Cl2—C19—Cl1108.1 (3)
C12—C7—P1122.38 (17)Cl2—C19—Cl3108.1 (3)
C8—C7—P1119.50 (17)Cl1—C19—Cl3107.2 (3)
C9—C8—C7120.6 (2)Cl2—C19—H19111.1
C9—C8—H8119.7Cl1—C19—H19111.1
C7—C8—H8119.7Cl3—C19—H19111.1
Br1—Pd1—P1—C1134.30 (8)C13—P1—C7—C850.5 (2)
Br1i—Pd1—P1—C1−47.44 (8)Pd1—P1—C7—C8−73.26 (19)
Br1—Pd1—P1—C13−104.60 (7)C12—C7—C8—C90.6 (4)
Br1i—Pd1—P1—C1373.65 (7)P1—C7—C8—C9−179.9 (2)
Br1—Pd1—P1—C714.74 (8)C7—C8—C9—C10−0.4 (4)
Br1i—Pd1—P1—C7−167.00 (8)C8—C9—C10—C110.4 (4)
C13—P1—C1—C611.4 (2)C9—C10—C11—C12−0.6 (4)
C7—P1—C1—C6−97.0 (2)C8—C7—C12—C11−0.9 (3)
Pd1—P1—C1—C6134.19 (17)P1—C7—C12—C11179.67 (18)
C13—P1—C1—C2−169.57 (17)C10—C11—C12—C70.9 (4)
C7—P1—C1—C282.00 (18)C1—P1—C13—C18112.87 (18)
Pd1—P1—C1—C2−46.79 (18)C7—P1—C13—C18−138.41 (18)
C6—C1—C2—C30.9 (3)Pd1—P1—C13—C18−9.6 (2)
P1—C1—C2—C3−178.16 (19)C1—P1—C13—C14−67.5 (2)
C1—C2—C3—C4−1.6 (4)C7—P1—C13—C1441.2 (2)
C2—C3—C4—C51.1 (4)Pd1—P1—C13—C14169.98 (16)
C3—C4—C5—C60.0 (4)C18—C13—C14—C15−2.0 (3)
C2—C1—C6—C50.2 (3)P1—C13—C14—C15178.35 (19)
P1—C1—C6—C5179.22 (18)C13—C14—C15—C160.2 (4)
C4—C5—C6—C1−0.7 (4)C14—C15—C16—C171.8 (4)
C1—P1—C7—C12−17.3 (2)C15—C16—C17—C18−2.1 (4)
C13—P1—C7—C12−130.09 (19)C14—C13—C18—C171.8 (3)
Pd1—P1—C7—C12106.19 (18)P1—C13—C18—C17−178.57 (17)
C1—P1—C7—C8163.24 (19)C16—C17—C18—C130.2 (4)

Symmetry codes: (i) −x+1, y, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2209).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2007). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Crawforth, C. M., Burling, S., Fairlamb, I. J. S., Kapdi, A. R., Taylor, R. J. K. & Whitwood, A. C. (2005). Tetrahedron, 61, 9736–9751.
  • Kubota, M., Ohba, S. & Saito, Y. (1991). Acta Cryst. C47, 1727–1729.
  • Rodríguez, N., de Arellano, C. M., Asensio, G. & Medio-Simón, M. (2007). Chem. Eur. J.13, 4223–4229. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Stark, J. L. & Whitmire, K. H. (1997). Acta Cryst. C53, IUC9700007.
  • Westrip, S. P. (2009). publCIF In preparation.

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