PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1564.
Published online 2009 November 14. doi:  10.1107/S1600536809045401
PMCID: PMC2971950

trans-Dibromidobis[diphen­yl(p-tol­yl)phosphine]palladium(II)

Abstract

In the title compound, [PdBr2(C19H17P)2], the PdII ion resides on a centre of symmetry and is coordinated by two Br anions [Pd—Br = 2.4266 (2) Å] and two P-donor ligands [Pd—P = 2.3462 (5) Å] in a slightly distorted square-planar geometry [P—Pd—Br = 93.528 (12)°]. Weak inter­molecular C—H(...)Br hydrogen bonds link mol­ecules into chains extended in [1An external file that holds a picture, illustration, etc.
Object name is e-65-m1564-efi1.jpg0].

Related literature

For the isostructural compound, trans-[PdCl2{P((Ph)2(p-Tol))}2], in which the Pd centers are coordinated by Cl anions instead of Br, see: Steyl et al. (2006 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1564-scheme1.jpg

Experimental

Crystal data

  • [PdBr2(C19H17P)2]
  • M r = 818.81
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1564-efi2.jpg
  • a = 10.0321 (4) Å
  • b = 10.0521 (4) Å
  • c = 10.2967 (4) Å
  • α = 70.876 (2)°
  • β = 68.288 (2)°
  • γ = 60.312 (2)°
  • V = 824.54 (6) Å3
  • Z = 1
  • Mo Kα radiation
  • μ = 3.11 mm−1
  • T = 100 K
  • 0.33 × 0.11 × 0.09 mm

Data collection

  • Bruker X8 APEXII 4K Kappa CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Bruker, 1998 [triangle]) T min = 0.427, T max = 0.767
  • 25915 measured reflections
  • 3982 independent reflections
  • 3621 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.021
  • wR(F 2) = 0.051
  • S = 1.04
  • 3982 reflections
  • 196 parameters
  • H-atom parameters constrained
  • Δρmax = 0.79 e Å−3
  • Δρmin = −0.46 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809045401/cv2640sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809045401/cv2640Isup2.hkl

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

Acknowledgments

Financial assistance from the University of the Free State 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.

supplementary crystallographic information

Comment

This study is aimed at expanding the knowledge of trans square-planar palladium complexes containing phosphine donor ligands and bromido or chlorido anions as coordinating atoms.

The title compound is centrosymmetric with a slightly distorted-square-planar geometry, as seen by the cis angle P—Pd—Br of 93.528 (12)°. The packing of the title compound is stabilized by two weak intermolecular C—H···Br hydrogen bonds (Table 1).

The corresponding chloro complex (Steyl et al., 2006) is iso-structural to the title complex when comparing the geometrical parameters as well as the crystallization mode. The RMS error of 0.061 Å also indicate the iso-structurality of the two complexes (the title complex superimposed with the corresponding dichloro-palladium complex (Steyl et al., 2006) including the Pd, Cl(Br), P and first C atoms of the phenyl rings).

Experimental

The title complex was synthesized by the addition of 2.2 equivalents of diphenyl(p-tolyl)phosphine (16 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 71%, 16 mg).

Refinement

All H atoms were positioned geometrically (C—H = 0.95 or 0.98 Å) and allowed to ride on their parent atoms, with Uiso(H) = (1.2 or 1.5) times Ueq of the parent atom, respectively. The s.u.'s on all the Cell Axes and all the Cell Angles are equal as calculated from the unit cell determination.

Figures

Fig. 1.
A sketch of the title compound showing the atomic numbering and 50% probability displacement ellipsoids [symmetry code: (i) 1 - x,1 - y,1 - z]. For the phenyl rings the first digit refers to ring number and the second digit to the atom in the ring. Hydrogen ...

Crystal data

[PdBr2(C19H17P)2]Z = 1
Mr = 818.81F(000) = 408
Triclinic, P1Dx = 1.649 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 10.0321 (4) ÅCell parameters from 6740 reflections
b = 10.0521 (4) Åθ = 2.4–28.3°
c = 10.2967 (4) ŵ = 3.11 mm1
α = 70.876 (2)°T = 100 K
β = 68.288 (2)°Cuboid, orange
γ = 60.312 (2)°0.33 × 0.11 × 0.09 mm
V = 824.54 (6) Å3

Data collection

Bruker X8 APEXII 4K Kappa CCD diffractometer3982 independent reflections
Radiation source: fine-focus sealed tube3621 reflections with I > 2σ(I)
graphiteRint = 0.029
Detector resolution: 512 pixels mm-1θmax = 28.0°, θmin = 2.4°
[var phi] and ω scansh = −13→13
Absorption correction: multi-scan (SADABS; Bruker, 1998)k = −13→13
Tmin = 0.427, Tmax = 0.767l = −13→13
25915 measured reflections

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)] = 0.021Hydrogen site location: riding model
wR(F2) = 0.051H-atom parameters constrained
S = 1.04w = 1/[σ2(Fo2) + (0.0199P)2 + 0.7898P] where P = (Fo2 + 2Fc2)/3
3982 reflections(Δ/σ)max = 0.001
196 parametersΔρmax = 0.79 e Å3
0 restraintsΔρmin = −0.46 e Å3

Special details

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)

xyzUiso*/Ueq
Pd0.50000.50000.50000.01341 (5)
Br0.39230 (2)0.78196 (2)0.45123 (2)0.02035 (6)
P0.28802 (5)0.49477 (5)0.69762 (5)0.01335 (9)
C110.3682 (2)0.3708 (2)0.84911 (18)0.0139 (3)
C120.4892 (2)0.3878 (2)0.8690 (2)0.0189 (4)
H120.52840.45730.80350.023*
C130.5507 (2)0.3014 (2)0.9859 (2)0.0195 (4)
H130.63010.31490.99860.023*
C140.4963 (2)0.1951 (2)1.0847 (2)0.0195 (4)
C150.3776 (2)0.1772 (2)1.0628 (2)0.0210 (4)
H150.34080.10531.12670.025*
C160.3131 (2)0.2648 (2)0.9470 (2)0.0178 (4)
H160.23270.25230.93510.021*
C1410.5660 (3)0.1007 (3)1.2101 (2)0.0332 (5)
H14A0.51450.03391.26700.050*
H14B0.55040.16931.26620.050*
H14C0.67740.03861.17720.050*
C210.1532 (2)0.4290 (2)0.68471 (19)0.0160 (3)
C220.2059 (2)0.3178 (2)0.6032 (2)0.0235 (4)
H220.31220.27430.55490.028*
C230.1014 (3)0.2714 (3)0.5934 (2)0.0281 (5)
H230.13860.19520.54040.034*
C24−0.0579 (2)0.3376 (2)0.6621 (2)0.0229 (4)
H24−0.12800.30710.65430.027*
C25−0.1120 (2)0.4490 (2)0.7422 (2)0.0225 (4)
H25−0.21920.49450.78780.027*
C26−0.0077 (2)0.4938 (2)0.7553 (2)0.0202 (4)
H26−0.04490.56730.81140.024*
C310.1493 (2)0.6787 (2)0.75882 (19)0.0144 (3)
C320.0568 (2)0.8003 (2)0.6700 (2)0.0181 (4)
H320.06970.78720.58010.022*
C33−0.0535 (2)0.9396 (2)0.7151 (2)0.0218 (4)
H33−0.11491.01960.65580.026*
C34−0.0728 (2)0.9604 (2)0.8489 (2)0.0224 (4)
H34−0.14641.05450.87880.027*
C350.0175 (2)0.8410 (2)0.9375 (2)0.0202 (4)
H350.00410.85471.02740.024*
C360.1286 (2)0.7006 (2)0.89275 (19)0.0160 (3)
H360.18920.62080.95270.019*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Pd0.01211 (9)0.01332 (9)0.01158 (9)−0.00500 (7)−0.00154 (7)−0.00073 (7)
Br0.01631 (9)0.01435 (9)0.02261 (10)−0.00509 (7)−0.00119 (7)−0.00071 (7)
P0.0124 (2)0.0147 (2)0.0114 (2)−0.00587 (17)−0.00238 (16)−0.00109 (16)
C110.0122 (8)0.0143 (8)0.0127 (8)−0.0038 (7)−0.0030 (6)−0.0027 (6)
C120.0188 (9)0.0186 (9)0.0207 (9)−0.0112 (7)−0.0061 (7)0.0014 (7)
C130.0189 (9)0.0206 (9)0.0229 (10)−0.0094 (8)−0.0088 (7)−0.0030 (8)
C140.0199 (9)0.0182 (9)0.0178 (9)−0.0057 (7)−0.0071 (7)−0.0016 (7)
C150.0210 (9)0.0222 (10)0.0191 (9)−0.0130 (8)−0.0051 (7)0.0035 (7)
C160.0158 (8)0.0197 (9)0.0183 (9)−0.0096 (7)−0.0046 (7)−0.0003 (7)
C1410.0392 (13)0.0362 (13)0.0271 (11)−0.0181 (11)−0.0190 (10)0.0065 (10)
C210.0177 (9)0.0173 (9)0.0138 (8)−0.0090 (7)−0.0068 (7)0.0021 (7)
C220.0188 (9)0.0258 (10)0.0261 (10)−0.0065 (8)−0.0061 (8)−0.0095 (8)
C230.0297 (11)0.0280 (11)0.0338 (12)−0.0112 (9)−0.0117 (9)−0.0119 (9)
C240.0278 (10)0.0268 (10)0.0216 (10)−0.0166 (9)−0.0132 (8)0.0028 (8)
C250.0198 (9)0.0285 (10)0.0198 (10)−0.0140 (8)−0.0048 (8)0.0008 (8)
C260.0202 (9)0.0249 (10)0.0169 (9)−0.0113 (8)−0.0024 (7)−0.0053 (8)
C310.0111 (8)0.0160 (8)0.0155 (8)−0.0073 (7)−0.0009 (6)−0.0024 (7)
C320.0161 (8)0.0214 (9)0.0151 (9)−0.0082 (7)−0.0039 (7)−0.0007 (7)
C330.0158 (9)0.0179 (9)0.0265 (10)−0.0063 (7)−0.0061 (8)0.0015 (8)
C340.0168 (9)0.0174 (9)0.0306 (11)−0.0067 (8)−0.0014 (8)−0.0079 (8)
C350.0194 (9)0.0238 (10)0.0213 (9)−0.0115 (8)−0.0015 (7)−0.0087 (8)
C360.0142 (8)0.0187 (9)0.0169 (9)−0.0095 (7)−0.0041 (7)−0.0012 (7)

Geometric parameters (Å, °)

Pd—P2.3462 (5)C21—C261.399 (3)
Pd—Pi2.3462 (5)C22—C231.387 (3)
Pd—Bri2.4266 (2)C22—H220.9300
Pd—Br2.4266 (2)C23—C241.384 (3)
P—C111.8150 (18)C23—H230.9300
P—C311.8217 (18)C24—C251.379 (3)
P—C211.8331 (19)C24—H240.9300
C11—C161.387 (3)C25—C261.388 (3)
C11—C121.399 (2)C25—H250.9300
C12—C131.385 (3)C26—H260.9300
C12—H120.9300C31—C361.391 (3)
C13—C141.389 (3)C31—C321.401 (3)
C13—H130.9300C32—C331.383 (3)
C14—C151.392 (3)C32—H320.9300
C14—C1411.505 (3)C33—C341.389 (3)
C15—C161.391 (3)C33—H330.9300
C15—H150.9300C34—C351.383 (3)
C16—H160.9300C34—H340.9300
C141—H14A0.9600C35—C361.391 (3)
C141—H14B0.9600C35—H350.9300
C141—H14C0.9600C36—H360.9300
C21—C221.390 (3)
P—Pd—Pi180.0C22—C21—C26118.53 (17)
P—Pd—Bri86.472 (12)C22—C21—P121.58 (14)
Pi—Pd—Bri93.528 (12)C26—C21—P119.87 (14)
P—Pd—Br93.528 (12)C23—C22—C21120.60 (19)
Pi—Pd—Br86.472 (12)C23—C22—H22119.7
Bri—Pd—Br180.0C21—C22—H22119.7
C11—P—C31103.51 (8)C24—C23—C22120.5 (2)
C11—P—C21107.56 (8)C24—C23—H23119.8
C31—P—C21101.59 (8)C22—C23—H23119.8
C11—P—Pd108.36 (6)C25—C24—C23119.51 (19)
C31—P—Pd116.57 (6)C25—C24—H24120.2
C21—P—Pd118.01 (6)C23—C24—H24120.2
C16—C11—C12118.91 (16)C24—C25—C26120.46 (19)
C16—C11—P123.69 (14)C24—C25—H25119.8
C12—C11—P117.36 (14)C26—C25—H25119.8
C13—C12—C11120.18 (17)C25—C26—C21120.41 (18)
C13—C12—H12119.9C25—C26—H26119.8
C11—C12—H12119.9C21—C26—H26119.8
C12—C13—C14121.38 (17)C36—C31—C32118.96 (17)
C12—C13—H13119.3C36—C31—P122.06 (14)
C14—C13—H13119.3C32—C31—P118.94 (14)
C13—C14—C15118.01 (17)C33—C32—C31120.42 (18)
C13—C14—C141120.66 (18)C33—C32—H32119.8
C15—C14—C141121.32 (18)C31—C32—H32119.8
C16—C15—C14121.24 (18)C32—C33—C34120.13 (18)
C16—C15—H15119.4C32—C33—H33119.9
C14—C15—H15119.4C34—C33—H33119.9
C11—C16—C15120.26 (17)C35—C34—C33119.91 (18)
C11—C16—H16119.9C35—C34—H34120.0
C15—C16—H16119.9C33—C34—H34120.0
C14—C141—H14A109.5C34—C35—C36120.19 (18)
C14—C141—H14B109.5C34—C35—H35119.9
H14A—C141—H14B109.5C36—C35—H35119.9
C14—C141—H14C109.5C31—C36—C35120.38 (17)
H14A—C141—H14C109.5C31—C36—H36119.8
H14B—C141—H14C109.5C35—C36—H36119.8
Bri—Pd—P—C1154.51 (6)C11—P—C21—C2690.47 (16)
Br—Pd—P—C11−125.49 (6)C31—P—C21—C26−17.89 (17)
Bri—Pd—P—C31170.70 (7)Pd—P—C21—C26−146.67 (13)
Br—Pd—P—C31−9.30 (7)C26—C21—C22—C23−0.6 (3)
Bri—Pd—P—C21−67.94 (7)P—C21—C22—C23−179.11 (16)
Br—Pd—P—C21112.06 (7)C21—C22—C23—C241.5 (3)
C31—P—C11—C1697.53 (16)C22—C23—C24—C25−0.9 (3)
C21—P—C11—C16−9.49 (18)C23—C24—C25—C26−0.6 (3)
Pd—P—C11—C16−138.11 (14)C24—C25—C26—C211.5 (3)
C31—P—C11—C12−80.59 (15)C22—C21—C26—C25−0.9 (3)
C21—P—C11—C12172.39 (14)P—C21—C26—C25177.67 (15)
Pd—P—C11—C1243.78 (15)C11—P—C31—C361.98 (17)
C16—C11—C12—C13−1.0 (3)C21—P—C31—C36113.45 (15)
P—C11—C12—C13177.24 (15)Pd—P—C31—C36−116.86 (14)
C11—C12—C13—C140.9 (3)C11—P—C31—C32−175.85 (14)
C12—C13—C14—C150.1 (3)C21—P—C31—C32−64.39 (16)
C12—C13—C14—C141179.2 (2)Pd—P—C31—C3265.30 (15)
C13—C14—C15—C16−1.1 (3)C36—C31—C32—C33−0.1 (3)
C141—C14—C15—C16179.83 (19)P—C31—C32—C33177.80 (14)
C12—C11—C16—C150.0 (3)C31—C32—C33—C340.4 (3)
P—C11—C16—C15−178.07 (15)C32—C33—C34—C35−0.6 (3)
C14—C15—C16—C111.0 (3)C33—C34—C35—C360.5 (3)
C11—P—C21—C22−91.04 (17)C32—C31—C36—C350.0 (3)
C31—P—C21—C22160.60 (16)P—C31—C36—C35−177.80 (14)
Pd—P—C21—C2231.82 (18)C34—C35—C36—C31−0.2 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C32—H32···Br0.932.993.2380 (18)97
C33—H33···Brii0.932.883.7498 (19)157
C22—H22···Bri0.932.713.501 (2)144

Symmetry codes: (ii) −x, −y+2, −z+1; (i) −x+1, −y+1, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2640).

References

  • 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. Bruker AXS Inc., Madison, Wisconsin, USA.
  • Sheldrick, G. M. (2008). Acta Cryst A64, 112–122. [PubMed]
  • Steyl, G., Kirsten, L. & Roodt, A. (2006). Acta Cryst. E62, m1705–m1707.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography