metal-organic compounds
trans-Dibromidobis[tris(4-chlorophenyl)phosphine]palladium(II)
aDepartment of Chemistry, University of the Free State, Bloemfontein 9300, South Africa
*Correspondence e-mail: leokirsten@gmail.com
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)°].
Related literature
The title compound is isostructural with the corresponding dichlorido complex, trans-[PdCl2{P(p-ClPh)3}2], see: Kolosova et al. (1986).
Experimental
Crystal data
|
Data collection: APEX2 (Bruker, 2005); cell 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.
Supporting information
10.1107/S1600536809045413/cv2637sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809045413/cv2637Isup2.hkl
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).
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).
Data collection: APEX2 (Bruker, 2005); cell
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).[PdBr2(C18H12Cl3P)2] | F(000) = 976 |
Mr = 997.41 | Dx = 1.776 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 7624 reflections |
a = 10.3453 (3) Å | θ = 2.3–28.4° |
b = 17.4489 (6) Å | µ = 3.18 mm−1 |
c = 10.6180 (4) Å | T = 100 K |
β = 103.385 (2)° | Cuboid, orange |
V = 1864.63 (11) Å3 | 0.33 × 0.30 × 0.25 mm |
Z = 2 |
Bruker X8 APEXII 4K Kappa CCD diffractometer | 4487 independent reflections |
Radiation source: fine-focus sealed tube | 3916 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.046 |
Detector resolution: 512 pixels mm-1 | θmax = 28.0°, θmin = 2.3° |
ϕ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −20→23 |
Tmin = 0.378, Tmax = 0.453 | l = −10→14 |
20106 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.026 | Hydrogen site location: riding model |
wR(F2) = 0.060 | H-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 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.74 e Å−3 |
[PdBr2(C18H12Cl3P)2] | V = 1864.63 (11) Å3 |
Mr = 997.41 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 10.3453 (3) Å | µ = 3.18 mm−1 |
b = 17.4489 (6) Å | T = 100 K |
c = 10.6180 (4) Å | 0.33 × 0.30 × 0.25 mm |
β = 103.385 (2)° |
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 = 0.453 | Rint = 0.046 |
20106 measured reflections |
R[F2 > 2σ(F2)] = 0.026 | 0 restraints |
wR(F2) = 0.060 | H-atom parameters constrained |
S = 1.04 | Δρmax = 0.67 e Å−3 |
4487 reflections | Δρmin = −0.74 e Å−3 |
214 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 | ||
Pd | 0.5000 | 0.5000 | 0.5000 | 0.01113 (6) | |
Br | 0.66195 (2) | 0.551557 (14) | 0.68290 (2) | 0.01764 (7) | |
P | 0.54624 (5) | 0.60598 (3) | 0.38405 (5) | 0.01106 (12) | |
C11 | 0.7244 (2) | 0.61782 (12) | 0.4023 (2) | 0.0121 (4) | |
C12 | 0.7977 (2) | 0.55569 (14) | 0.3742 (2) | 0.0181 (5) | |
H12 | 0.7539 | 0.5087 | 0.3466 | 0.022* | |
C13 | 0.9335 (2) | 0.56171 (14) | 0.3862 (2) | 0.0202 (5) | |
H13 | 0.9827 | 0.5200 | 0.3637 | 0.024* | |
C14 | 0.9961 (2) | 0.62964 (14) | 0.4314 (2) | 0.0167 (5) | |
C15 | 0.9267 (2) | 0.69103 (14) | 0.4626 (2) | 0.0180 (5) | |
H15 | 0.9716 | 0.7371 | 0.4943 | 0.022* | |
C16 | 0.7899 (2) | 0.68506 (13) | 0.4474 (2) | 0.0166 (5) | |
H16 | 0.7410 | 0.7274 | 0.4682 | 0.020* | |
Cl1 | 1.16679 (6) | 0.63849 (4) | 0.44886 (6) | 0.02709 (15) | |
C21 | 0.4895 (2) | 0.69919 (13) | 0.4282 (2) | 0.0127 (4) | |
C22 | 0.4671 (2) | 0.71256 (14) | 0.5508 (2) | 0.0165 (5) | |
H22 | 0.4778 | 0.6720 | 0.6121 | 0.020* | |
C23 | 0.4291 (2) | 0.78460 (14) | 0.5841 (2) | 0.0193 (5) | |
H23 | 0.4141 | 0.7936 | 0.6678 | 0.023* | |
C24 | 0.4134 (2) | 0.84297 (13) | 0.4944 (2) | 0.0158 (5) | |
C25 | 0.4340 (2) | 0.83135 (14) | 0.3719 (2) | 0.0169 (5) | |
H25 | 0.4222 | 0.8721 | 0.3109 | 0.020* | |
C26 | 0.4722 (2) | 0.75940 (13) | 0.3396 (2) | 0.0160 (5) | |
H26 | 0.4869 | 0.7509 | 0.2557 | 0.019* | |
Cl2 | 0.36890 (6) | 0.93429 (3) | 0.53545 (6) | 0.02335 (14) | |
C31 | 0.4774 (2) | 0.60521 (12) | 0.2097 (2) | 0.0123 (4) | |
C32 | 0.3402 (2) | 0.61279 (13) | 0.1658 (2) | 0.0151 (5) | |
H32 | 0.2860 | 0.6153 | 0.2267 | 0.018* | |
C33 | 0.2820 (2) | 0.61675 (13) | 0.0353 (2) | 0.0154 (5) | |
H33 | 0.1885 | 0.6221 | 0.0059 | 0.018* | |
C34 | 0.3626 (2) | 0.61276 (12) | −0.0525 (2) | 0.0150 (5) | |
C35 | 0.4977 (2) | 0.60225 (13) | −0.0127 (2) | 0.0170 (5) | |
H35 | 0.5508 | 0.5975 | −0.0743 | 0.020* | |
C36 | 0.5555 (2) | 0.59876 (13) | 0.1195 (2) | 0.0151 (5) | |
H36 | 0.6488 | 0.5919 | 0.1483 | 0.018* | |
Cl3 | 0.28975 (6) | 0.62480 (3) | −0.21644 (5) | 0.02222 (13) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Pd | 0.01157 (11) | 0.01282 (13) | 0.00824 (12) | −0.00270 (9) | 0.00075 (8) | 0.00108 (9) |
Br | 0.01929 (12) | 0.01956 (13) | 0.01117 (12) | −0.00653 (9) | −0.00241 (9) | 0.00144 (9) |
P | 0.0110 (3) | 0.0124 (3) | 0.0096 (3) | −0.0017 (2) | 0.0020 (2) | 0.0013 (2) |
C11 | 0.0124 (10) | 0.0127 (11) | 0.0109 (10) | −0.0004 (8) | 0.0019 (8) | 0.0035 (8) |
C12 | 0.0186 (11) | 0.0145 (12) | 0.0192 (12) | 0.0000 (9) | 0.0002 (9) | −0.0033 (9) |
C13 | 0.0218 (12) | 0.0213 (13) | 0.0168 (12) | 0.0098 (10) | 0.0033 (10) | −0.0025 (10) |
C14 | 0.0118 (10) | 0.0272 (13) | 0.0112 (11) | 0.0012 (10) | 0.0027 (8) | 0.0019 (9) |
C15 | 0.0157 (11) | 0.0157 (12) | 0.0229 (13) | −0.0039 (9) | 0.0051 (9) | −0.0008 (9) |
C16 | 0.0153 (11) | 0.0121 (11) | 0.0237 (13) | 0.0013 (9) | 0.0069 (9) | 0.0000 (9) |
Cl1 | 0.0114 (3) | 0.0469 (4) | 0.0236 (3) | 0.0021 (3) | 0.0054 (2) | 0.0013 (3) |
C21 | 0.0094 (10) | 0.0157 (12) | 0.0126 (11) | −0.0022 (8) | 0.0020 (8) | −0.0005 (9) |
C22 | 0.0165 (11) | 0.0195 (12) | 0.0149 (11) | −0.0026 (9) | 0.0062 (9) | 0.0029 (9) |
C23 | 0.0200 (12) | 0.0221 (13) | 0.0184 (12) | −0.0005 (10) | 0.0099 (10) | −0.0033 (10) |
C24 | 0.0105 (10) | 0.0146 (12) | 0.0235 (12) | −0.0017 (9) | 0.0065 (9) | −0.0043 (9) |
C25 | 0.0155 (11) | 0.0181 (12) | 0.0168 (11) | 0.0004 (9) | 0.0030 (9) | 0.0033 (9) |
C26 | 0.0176 (11) | 0.0189 (12) | 0.0124 (11) | 0.0009 (9) | 0.0054 (9) | 0.0009 (9) |
Cl2 | 0.0251 (3) | 0.0184 (3) | 0.0303 (3) | 0.0016 (2) | 0.0141 (3) | −0.0046 (2) |
C31 | 0.0165 (11) | 0.0090 (11) | 0.0110 (10) | −0.0012 (8) | 0.0022 (8) | 0.0011 (8) |
C32 | 0.0166 (11) | 0.0169 (12) | 0.0125 (11) | −0.0008 (9) | 0.0050 (9) | 0.0017 (9) |
C33 | 0.0152 (11) | 0.0128 (12) | 0.0164 (11) | −0.0010 (9) | 0.0002 (9) | 0.0021 (9) |
C34 | 0.0247 (12) | 0.0098 (11) | 0.0082 (10) | −0.0006 (9) | −0.0006 (9) | −0.0015 (8) |
C35 | 0.0237 (12) | 0.0161 (12) | 0.0131 (11) | 0.0016 (9) | 0.0079 (9) | −0.0009 (9) |
C36 | 0.0156 (11) | 0.0151 (12) | 0.0158 (11) | 0.0016 (9) | 0.0058 (9) | 0.0005 (9) |
Cl3 | 0.0325 (3) | 0.0227 (3) | 0.0093 (3) | 0.0015 (3) | 0.0003 (2) | −0.0014 (2) |
Pd—Pi | 2.3317 (6) | C22—C23 | 1.387 (3) |
Pd—P | 2.3317 (6) | C22—H22 | 0.9500 |
Pd—Br | 2.4252 (2) | C23—C24 | 1.378 (3) |
Pd—Bri | 2.4252 (2) | C23—H23 | 0.9500 |
P—C11 | 1.820 (2) | C24—C25 | 1.381 (3) |
P—C31 | 1.823 (2) | C24—Cl2 | 1.742 (2) |
P—C21 | 1.827 (2) | C25—C26 | 1.383 (3) |
C11—C16 | 1.384 (3) | C25—H25 | 0.9500 |
C11—C12 | 1.394 (3) | C26—H26 | 0.9500 |
C12—C13 | 1.386 (3) | C31—C36 | 1.393 (3) |
C12—H12 | 0.9500 | C31—C32 | 1.394 (3) |
C13—C14 | 1.382 (3) | C32—C33 | 1.379 (3) |
C13—H13 | 0.9500 | C32—H32 | 0.9500 |
C14—C15 | 1.372 (3) | C33—C34 | 1.389 (3) |
C14—Cl1 | 1.739 (2) | C33—H33 | 0.9500 |
C15—C16 | 1.391 (3) | C34—C35 | 1.376 (3) |
C15—H15 | 0.9500 | C34—Cl3 | 1.742 (2) |
C16—H16 | 0.9500 | C35—C36 | 1.394 (3) |
C21—C26 | 1.394 (3) | C35—H35 | 0.9500 |
C21—C22 | 1.395 (3) | C36—H36 | 0.9500 |
Pi—Pd—P | 180.000 (17) | C23—C22—C21 | 120.5 (2) |
Pi—Pd—Br | 93.411 (15) | C23—C22—H22 | 119.7 |
P—Pd—Br | 86.589 (15) | C21—C22—H22 | 119.7 |
Pi—Pd—Bri | 86.589 (15) | C24—C23—C22 | 119.3 (2) |
P—Pd—Bri | 93.411 (15) | C24—C23—H23 | 120.4 |
Br—Pd—Bri | 180.000 (10) | C22—C23—H23 | 120.4 |
C11—P—C31 | 104.88 (10) | C23—C24—C25 | 121.6 (2) |
C11—P—C21 | 104.43 (10) | C23—C24—Cl2 | 119.94 (17) |
C31—P—C21 | 101.18 (10) | C25—C24—Cl2 | 118.50 (18) |
C11—P—Pd | 111.12 (7) | C24—C25—C26 | 118.8 (2) |
C31—P—Pd | 116.79 (7) | C24—C25—H25 | 120.6 |
C21—P—Pd | 116.95 (7) | C26—C25—H25 | 120.6 |
C16—C11—C12 | 119.1 (2) | C25—C26—C21 | 121.1 (2) |
C16—C11—P | 122.37 (17) | C25—C26—H26 | 119.5 |
C12—C11—P | 118.44 (17) | C21—C26—H26 | 119.5 |
C13—C12—C11 | 120.8 (2) | C36—C31—C32 | 119.1 (2) |
C13—C12—H12 | 119.6 | C36—C31—P | 123.10 (17) |
C11—C12—H12 | 119.6 | C32—C31—P | 117.81 (16) |
C14—C13—C12 | 118.7 (2) | C33—C32—C31 | 121.0 (2) |
C14—C13—H13 | 120.6 | C33—C32—H32 | 119.5 |
C12—C13—H13 | 120.6 | C31—C32—H32 | 119.5 |
C15—C14—C13 | 121.6 (2) | C32—C33—C34 | 118.8 (2) |
C15—C14—Cl1 | 118.69 (18) | C32—C33—H33 | 120.6 |
C13—C14—Cl1 | 119.69 (18) | C34—C33—H33 | 120.6 |
C14—C15—C16 | 119.3 (2) | C35—C34—C33 | 121.7 (2) |
C14—C15—H15 | 120.4 | C35—C34—Cl3 | 119.80 (17) |
C16—C15—H15 | 120.4 | C33—C34—Cl3 | 118.46 (18) |
C11—C16—C15 | 120.5 (2) | C34—C35—C36 | 118.9 (2) |
C11—C16—H16 | 119.8 | C34—C35—H35 | 120.5 |
C15—C16—H16 | 119.8 | C36—C35—H35 | 120.5 |
C26—C21—C22 | 118.8 (2) | C31—C36—C35 | 120.4 (2) |
C26—C21—P | 119.79 (16) | C31—C36—H36 | 119.8 |
C22—C21—P | 121.43 (17) | C35—C36—H36 | 119.8 |
Br—Pd—P—C11 | 49.81 (8) | Pd—P—C21—C22 | 23.8 (2) |
Bri—Pd—P—C11 | −130.19 (8) | C26—C21—C22—C23 | −0.4 (3) |
Br—Pd—P—C31 | 170.03 (8) | P—C21—C22—C23 | 177.41 (17) |
Bri—Pd—P—C31 | −9.97 (8) | C21—C22—C23—C24 | 0.2 (3) |
Br—Pd—P—C21 | −69.94 (8) | C22—C23—C24—C25 | 0.3 (3) |
Bri—Pd—P—C21 | 110.06 (8) | C22—C23—C24—Cl2 | −178.76 (17) |
C31—P—C11—C16 | 109.0 (2) | C23—C24—C25—C26 | −0.4 (3) |
C21—P—C11—C16 | 3.0 (2) | Cl2—C24—C25—C26 | 178.59 (17) |
Pd—P—C11—C16 | −123.98 (18) | C24—C25—C26—C21 | 0.2 (3) |
C31—P—C11—C12 | −73.49 (19) | C22—C21—C26—C25 | 0.2 (3) |
C21—P—C11—C12 | −179.49 (17) | P—C21—C26—C25 | −177.63 (17) |
Pd—P—C11—C12 | 53.56 (19) | C11—P—C31—C36 | 11.9 (2) |
C16—C11—C12—C13 | −2.6 (3) | C21—P—C31—C36 | 120.28 (19) |
P—C11—C12—C13 | 179.82 (18) | Pd—P—C31—C36 | −111.59 (18) |
C11—C12—C13—C14 | 2.5 (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—Cl1 | 179.37 (18) | Pd—P—C31—C32 | 69.53 (18) |
C13—C14—C15—C16 | −0.6 (4) | C36—C31—C32—C33 | −2.4 (3) |
Cl1—C14—C15—C16 | 179.15 (18) | P—C31—C32—C33 | 176.56 (18) |
C12—C11—C16—C15 | 1.0 (3) | C31—C32—C33—C34 | 0.2 (3) |
P—C11—C16—C15 | 178.56 (17) | C32—C33—C34—C35 | 2.4 (3) |
C14—C15—C16—C11 | 0.5 (3) | C32—C33—C34—Cl3 | −175.38 (17) |
C11—P—C21—C26 | 78.41 (19) | C33—C34—C35—C36 | −2.7 (3) |
C31—P—C21—C26 | −30.3 (2) | Cl3—C34—C35—C36 | 175.00 (18) |
Pd—P—C21—C26 | −158.34 (15) | C32—C31—C36—C35 | 2.0 (3) |
C11—P—C21—C22 | −99.40 (19) | P—C31—C36—C35 | −176.87 (17) |
C31—P—C21—C22 | 151.87 (18) | C34—C35—C36—C31 | 0.5 (3) |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [PdBr2(C18H12Cl3P)2] |
Mr | 997.41 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 100 |
a, b, c (Å) | 10.3453 (3), 17.4489 (6), 10.6180 (4) |
β (°) | 103.385 (2) |
V (Å3) | 1864.63 (11) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.18 |
Crystal size (mm) | 0.33 × 0.30 × 0.25 |
Data collection | |
Diffractometer | Bruker X8 APEXII 4K Kappa CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.378, 0.453 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 20106, 4487, 3916 |
Rint | 0.046 |
(sin θ/λ)max (Å−1) | 0.661 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.026, 0.060, 1.04 |
No. of reflections | 4487 |
No. of parameters | 214 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.67, −0.74 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2004), SAINT-Plus and XPREP (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), DIAMOND (Brandenburg & Putz, 2006).
Acknowledgements
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
Brandenburg, K. & Putz, H. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (1998). SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2004). SAINT-Plus (including XPREP). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bruker (2005). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
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. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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).