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Acta Cryst. (2009). E65, m1565    [ doi:10.1107/S1600536809045413 ]

trans-Dibromidobis[tris(4-chlorophenyl)phosphine]palladium(II)

L. Kirsten and G. Steyl

Abstract top

In the title compound, [PdBr2(C18H12Cl3P)2], the PdII ion is situated on a centre of symmetry and is coordinated by two Br anions [Pd-Br = 2.4252 (2) Å] and two P-donor ligands [Pd-P = 2.3317 (6) Å] in a slightly distorted square-planar geometry [P-Pd-Br = 86.589 (15)°].

Comment top

The title compound, (I), is one of a few literature structures containing a Pd centre coordinated by to Br atoms and two P donor ligands in a trans configuration. Our research is aimed at expanding the number of known structures of the aforementioned type and to finally generalize on the crystallization mode, if any, of these complexes.

The molecule of (I) (Fig. 1), is centrosymmetric with pairs of equivalent P donor ligands trans to one another in a slightly distorted square-planar geometry [P—Pd—Br 86.589 (15)°].

The corresponding chloro complex (Kolosova et al., 1986) is iso-structural to (I) when comparing the geometrical parameters. The RMS error of 0.097 Å also indicate the iso-structurality of the two complexes (the title complex superimposed with the corresponding dichloro-palladium complex (Kolosova et al., 1986) including all the atoms except the hydrogen atoms).

Related literature top

The title compound is isostructural with the corresponding dichloro complex, trans-[PdCl2{P(p-ClPh)3}2], see: Kolosova et al. (1986).

Experimental top

The title complex was synthesized by the addition of 2.2 equivalents of tris(4-Cl-phenyl)-phosphine (21 mg, 0.059 mmol) to [Pd(COD)Br2] (10 mg, 0.026 mmol) in 10 ml of dichloromethane while stirring for 5 minutes. Slow evaporation of the solvent resulted in orange crystals suitable for X-Ray diffraction (yield 74%, 19 mg).

Refinement top

All H atoms were positioned geometrically and allowed to ride on their parent atoms, with C—H = 0.95 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT-Plus (Bruker, 2004); data reduction: SAINT-Plus and XPREP (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg & Putz, 2006); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. Representation of the title compound, showing the numbering scheme and displacement ellipsoids (50% probability). For the carbon rings, the first digit refers to ring number, second digit to atom in the ring. Hydrogen atoms omitted for clarity [symmetry code: (i) 1 - x,1 - y,1 - z].
trans-Dibromidobis[tris(4-chlorophenyl)phosphine]palladium(II) top
Crystal data top
[PdBr2(C18H12Cl3P)2]F(000) = 976
Mr = 997.41Dx = 1.776 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 7624 reflections
a = 10.3453 (3) Åθ = 2.3–28.4°
b = 17.4489 (6) ŵ = 3.18 mm−1
c = 10.6180 (4) ÅT = 100 K
β = 103.385 (2)°Cuboid, orange
V = 1864.63 (11) Å30.33 × 0.30 × 0.25 mm
Z = 2
Data collection top
Bruker X8 APEXII 4K Kappa CCD
diffractometer		4487 independent reflections
Radiation source: fine-focus sealed tube3916 reflections with I > 2σ(I)
graphiteRint = 0.046
Detector resolution: 512 pixels mm-1θmax = 28.0°, θmin = 2.3°
φ and ω scansh = −13→13
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		k = −20→23
Tmin = 0.378, Tmax = 0.453l = −10→14
20106 measured reflections
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)] = 0.026Hydrogen site location: riding model
wR(F2) = 0.060H-atom parameters constrained
S = 1.04 w = 1/[σ2(Fo2) + (0.0187P)2 + 1.3608P]
where P = (Fo2 + 2Fc2)/3
4487 reflections(Δ/σ)max = 0.002
214 parametersΔρmax = 0.67 e Å−3
0 restraintsΔρmin = −0.74 e Å−3
Crystal data top
[PdBr2(C18H12Cl3P)2]V = 1864.63 (11) Å3
Mr = 997.41Z = 2
Monoclinic, P21/nMo Kα radiation
a = 10.3453 (3) ŵ = 3.18 mm−1
b = 17.4489 (6) ÅT = 100 K
c = 10.6180 (4) Å0.33 × 0.30 × 0.25 mm
β = 103.385 (2)°
Data collection top
Bruker X8 APEXII 4K Kappa CCD
diffractometer		4487 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		3916 reflections with I > 2σ(I)
Tmin = 0.378, Tmax = 0.453Rint = 0.046
20106 measured reflectionsθmax = 28.0°
Refinement top
R[F2 > 2σ(F2)] = 0.026H-atom parameters constrained
wR(F2) = 0.060Δρmax = 0.67 e Å−3
S = 1.04Δρmin = −0.74 e Å−3
4487 reflectionsAbsolute structure: ?
214 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Special details top

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*/Ueq
Pd0.50000.50000.50000.01113 (6)
Br0.66195 (2)0.551557 (14)0.68290 (2)0.01764 (7)
P0.54624 (5)0.60598 (3)0.38405 (5)0.01106 (12)
C110.7244 (2)0.61782 (12)0.4023 (2)0.0121 (4)
C120.7977 (2)0.55569 (14)0.3742 (2)0.0181 (5)
H120.75390.50870.34660.022*
C130.9335 (2)0.56171 (14)0.3862 (2)0.0202 (5)
H130.98270.52000.36370.024*
C140.9961 (2)0.62964 (14)0.4314 (2)0.0167 (5)
C150.9267 (2)0.69103 (14)0.4626 (2)0.0180 (5)
H150.97160.73710.49430.022*
C160.7899 (2)0.68506 (13)0.4474 (2)0.0166 (5)
H160.74100.72740.46820.020*
Cl11.16679 (6)0.63849 (4)0.44886 (6)0.02709 (15)
C210.4895 (2)0.69919 (13)0.4282 (2)0.0127 (4)
C220.4671 (2)0.71256 (14)0.5508 (2)0.0165 (5)
H220.47780.67200.61210.020*
C230.4291 (2)0.78460 (14)0.5841 (2)0.0193 (5)
H230.41410.79360.66780.023*
C240.4134 (2)0.84297 (13)0.4944 (2)0.0158 (5)
C250.4340 (2)0.83135 (14)0.3719 (2)0.0169 (5)
H250.42220.87210.31090.020*
C260.4722 (2)0.75940 (13)0.3396 (2)0.0160 (5)
H260.48690.75090.25570.019*
Cl20.36890 (6)0.93429 (3)0.53545 (6)0.02335 (14)
C310.4774 (2)0.60521 (12)0.2097 (2)0.0123 (4)
C320.3402 (2)0.61279 (13)0.1658 (2)0.0151 (5)
H320.28600.61530.22670.018*
C330.2820 (2)0.61675 (13)0.0353 (2)0.0154 (5)
H330.18850.62210.00590.018*
C340.3626 (2)0.61276 (12)−0.0525 (2)0.0150 (5)
C350.4977 (2)0.60225 (13)−0.0127 (2)0.0170 (5)
H350.55080.5975−0.07430.020*
C360.5555 (2)0.59876 (13)0.1195 (2)0.0151 (5)
H360.64880.59190.14830.018*
Cl30.28975 (6)0.62480 (3)−0.21644 (5)0.02222 (13)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd0.01157 (11)0.01282 (13)0.00824 (12)−0.00270 (9)0.00075 (8)0.00108 (9)
Br0.01929 (12)0.01956 (13)0.01117 (12)−0.00653 (9)−0.00241 (9)0.00144 (9)
P0.0110 (3)0.0124 (3)0.0096 (3)−0.0017 (2)0.0020 (2)0.0013 (2)
C110.0124 (10)0.0127 (11)0.0109 (10)−0.0004 (8)0.0019 (8)0.0035 (8)
C120.0186 (11)0.0145 (12)0.0192 (12)0.0000 (9)0.0002 (9)−0.0033 (9)
C130.0218 (12)0.0213 (13)0.0168 (12)0.0098 (10)0.0033 (10)−0.0025 (10)
C140.0118 (10)0.0272 (13)0.0112 (11)0.0012 (10)0.0027 (8)0.0019 (9)
C150.0157 (11)0.0157 (12)0.0229 (13)−0.0039 (9)0.0051 (9)−0.0008 (9)
C160.0153 (11)0.0121 (11)0.0237 (13)0.0013 (9)0.0069 (9)0.0000 (9)
Cl10.0114 (3)0.0469 (4)0.0236 (3)0.0021 (3)0.0054 (2)0.0013 (3)
C210.0094 (10)0.0157 (12)0.0126 (11)−0.0022 (8)0.0020 (8)−0.0005 (9)
C220.0165 (11)0.0195 (12)0.0149 (11)−0.0026 (9)0.0062 (9)0.0029 (9)
C230.0200 (12)0.0221 (13)0.0184 (12)−0.0005 (10)0.0099 (10)−0.0033 (10)
C240.0105 (10)0.0146 (12)0.0235 (12)−0.0017 (9)0.0065 (9)−0.0043 (9)
C250.0155 (11)0.0181 (12)0.0168 (11)0.0004 (9)0.0030 (9)0.0033 (9)
C260.0176 (11)0.0189 (12)0.0124 (11)0.0009 (9)0.0054 (9)0.0009 (9)
Cl20.0251 (3)0.0184 (3)0.0303 (3)0.0016 (2)0.0141 (3)−0.0046 (2)
C310.0165 (11)0.0090 (11)0.0110 (10)−0.0012 (8)0.0022 (8)0.0011 (8)
C320.0166 (11)0.0169 (12)0.0125 (11)−0.0008 (9)0.0050 (9)0.0017 (9)
C330.0152 (11)0.0128 (12)0.0164 (11)−0.0010 (9)0.0002 (9)0.0021 (9)
C340.0247 (12)0.0098 (11)0.0082 (10)−0.0006 (9)−0.0006 (9)−0.0015 (8)
C350.0237 (12)0.0161 (12)0.0131 (11)0.0016 (9)0.0079 (9)−0.0009 (9)
C360.0156 (11)0.0151 (12)0.0158 (11)0.0016 (9)0.0058 (9)0.0005 (9)
Cl30.0325 (3)0.0227 (3)0.0093 (3)0.0015 (3)0.0003 (2)−0.0014 (2)
Geometric parameters (Å, °) top
Pd—Pi2.3317 (6)C22—C231.387 (3)
Pd—P2.3317 (6)C22—H220.9500
Pd—Br2.4252 (2)C23—C241.378 (3)
Pd—Bri2.4252 (2)C23—H230.9500
P—C111.820 (2)C24—C251.381 (3)
P—C311.823 (2)C24—Cl21.742 (2)
P—C211.827 (2)C25—C261.383 (3)
C11—C161.384 (3)C25—H250.9500
C11—C121.394 (3)C26—H260.9500
C12—C131.386 (3)C31—C361.393 (3)
C12—H120.9500C31—C321.394 (3)
C13—C141.382 (3)C32—C331.379 (3)
C13—H130.9500C32—H320.9500
C14—C151.372 (3)C33—C341.389 (3)
C14—Cl11.739 (2)C33—H330.9500
C15—C161.391 (3)C34—C351.376 (3)
C15—H150.9500C34—Cl31.742 (2)
C16—H160.9500C35—C361.394 (3)
C21—C261.394 (3)C35—H350.9500
C21—C221.395 (3)C36—H360.9500
Pi—Pd—P180.000 (17)C23—C22—C21120.5 (2)
Pi—Pd—Br93.411 (15)C23—C22—H22119.7
P—Pd—Br86.589 (15)C21—C22—H22119.7
Pi—Pd—Bri86.589 (15)C24—C23—C22119.3 (2)
P—Pd—Bri93.411 (15)C24—C23—H23120.4
Br—Pd—Bri180.000 (10)C22—C23—H23120.4
C11—P—C31104.88 (10)C23—C24—C25121.6 (2)
C11—P—C21104.43 (10)C23—C24—Cl2119.94 (17)
C31—P—C21101.18 (10)C25—C24—Cl2118.50 (18)
C11—P—Pd111.12 (7)C24—C25—C26118.8 (2)
C31—P—Pd116.79 (7)C24—C25—H25120.6
C21—P—Pd116.95 (7)C26—C25—H25120.6
C16—C11—C12119.1 (2)C25—C26—C21121.1 (2)
C16—C11—P122.37 (17)C25—C26—H26119.5
C12—C11—P118.44 (17)C21—C26—H26119.5
C13—C12—C11120.8 (2)C36—C31—C32119.1 (2)
C13—C12—H12119.6C36—C31—P123.10 (17)
C11—C12—H12119.6C32—C31—P117.81 (16)
C14—C13—C12118.7 (2)C33—C32—C31121.0 (2)
C14—C13—H13120.6C33—C32—H32119.5
C12—C13—H13120.6C31—C32—H32119.5
C15—C14—C13121.6 (2)C32—C33—C34118.8 (2)
C15—C14—Cl1118.69 (18)C32—C33—H33120.6
C13—C14—Cl1119.69 (18)C34—C33—H33120.6
C14—C15—C16119.3 (2)C35—C34—C33121.7 (2)
C14—C15—H15120.4C35—C34—Cl3119.80 (17)
C16—C15—H15120.4C33—C34—Cl3118.46 (18)
C11—C16—C15120.5 (2)C34—C35—C36118.9 (2)
C11—C16—H16119.8C34—C35—H35120.5
C15—C16—H16119.8C36—C35—H35120.5
C26—C21—C22118.8 (2)C31—C36—C35120.4 (2)
C26—C21—P119.79 (16)C31—C36—H36119.8
C22—C21—P121.43 (17)C35—C36—H36119.8
Br—Pd—P—C1149.81 (8)Pd—P—C21—C2223.8 (2)
Bri—Pd—P—C11−130.19 (8)C26—C21—C22—C23−0.4 (3)
Br—Pd—P—C31170.03 (8)P—C21—C22—C23177.41 (17)
Bri—Pd—P—C31−9.97 (8)C21—C22—C23—C240.2 (3)
Br—Pd—P—C21−69.94 (8)C22—C23—C24—C250.3 (3)
Bri—Pd—P—C21110.06 (8)C22—C23—C24—Cl2−178.76 (17)
C31—P—C11—C16109.0 (2)C23—C24—C25—C26−0.4 (3)
C21—P—C11—C163.0 (2)Cl2—C24—C25—C26178.59 (17)
Pd—P—C11—C16−123.98 (18)C24—C25—C26—C210.2 (3)
C31—P—C11—C12−73.49 (19)C22—C21—C26—C250.2 (3)
C21—P—C11—C12−179.49 (17)P—C21—C26—C25−177.63 (17)
Pd—P—C11—C1253.56 (19)C11—P—C31—C3611.9 (2)
C16—C11—C12—C13−2.6 (3)C21—P—C31—C36120.28 (19)
P—C11—C12—C13179.82 (18)Pd—P—C31—C36−111.59 (18)
C11—C12—C13—C142.5 (4)C11—P—C31—C32−166.98 (17)
C12—C13—C14—C15−0.9 (4)C21—P—C31—C32−58.60 (19)
C12—C13—C14—Cl1179.37 (18)Pd—P—C31—C3269.53 (18)
C13—C14—C15—C16−0.6 (4)C36—C31—C32—C33−2.4 (3)
Cl1—C14—C15—C16179.15 (18)P—C31—C32—C33176.56 (18)
C12—C11—C16—C151.0 (3)C31—C32—C33—C340.2 (3)
P—C11—C16—C15178.56 (17)C32—C33—C34—C352.4 (3)
C14—C15—C16—C110.5 (3)C32—C33—C34—Cl3−175.38 (17)
C11—P—C21—C2678.41 (19)C33—C34—C35—C36−2.7 (3)
C31—P—C21—C26−30.3 (2)Cl3—C34—C35—C36175.00 (18)
Pd—P—C21—C26−158.34 (15)C32—C31—C36—C352.0 (3)
C11—P—C21—C22−99.40 (19)P—C31—C36—C35−176.87 (17)
C31—P—C21—C22151.87 (18)C34—C35—C36—C310.5 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Acknowledgements top

Financial assistance from the University of the Free State and Professor A. Roodt is gratefully acknowledged. Part of this material is based on work supported by the South African National Research Foundation (NRF) under grant No. GUN 2068915.

references
References top

Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Bruker (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2004). SAINT-Plus (including XPREP). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2005). APEX2. Version 1.0-27. Bruker AXS Inc., Madison, Wisconsin, USA.

Kolosova, N. D., Sobolev, A. N., Kron, T. E., Petrov, E. S. & Bel'skii, V. K. (1986). Koord. Khim. (Russ.) (Coord. Chem.), 12, 393–399.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.