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Acta Cryst. (2008). E64, m1349    [ doi:10.1107/S1600536808030845 ]

Dibromidobis[2-(dicyclohexylphosphanyl)biphenyl-[kappa]P]palladium(II)

C. Xu, Y.-F. Li, Z.-Q. Wang, F.-F. Cen and Y.-Q. Zhang

Abstract top

The title compound, [PdBr2(C24H31P)2], has a distorted trans square-planar coordination of the Pd atom, which occupies an inversion centre. The most important bond distances include Pd-P of 2.380 (2) Å and Pd-Br of 2.515 (2) Å. Weak intermolecular [pi]-[pi] interactions between the benzene rings of adjacent molecules [centroid-centroid distance = 3.949 (6) Å] are present via crystallographic inversion centres, resulting in a one-dimensional supramolecular architecture.

Comment top

Phosphine complexes of palladium have widely been used as catalysts for various reactions (Tsuji, 1995). These complexes are easily prepared from palladium(II) salts and an excess of phosphine ligands. Among them, monophosphinobiaryl complexes of palladium are one of the most important ones (Barder et al., 2005; Christmann et al., 2006; Xu et al., 2007).

The title complex has crystallographic inversion symmetry Ci (Fig.1). The Pd atom is in a square-planar environment, while the trans 2-(Dicyclohexylphosphanyl)biphenyl ligands are in an eclipsed conformation. The dihedral angles of the benzene rings are 60.8 (2)°. The Pd—P [2.380 (2) Å] and Pd—Br [2.515 (5) Å] bond lengths are longer than the related triphenylphosphine complex of palladium [2.336 (2)Å and 2.4169 (13) Å](Stark & Whitmire, 1997) possibly due to the steric bulk of the ligand. Weak intermolecular π···π interactions between the benzene rings C19 - C24 (Cg4) of inversion related adjacent molecules [centroid-centroid distance Cg4···Cg4ii is 3.949 (6) Å, the perpendicular distance Cg4 on ring Cg4ii is 3.582 Å, and the slippage is 1.663 Å, symmetry code ii = 1 - x, 1 - y, 1 - z] were calculated for the structure of the title complex with the programme PLATON (Spek, 2003), resulting in a one-dimensional supramolecular architecture.

Related literature top

For related literature, see: Barder et al. (2005); Christmann et al. (2006); Stark & Whitmire (1997); Tomori et al. (2000); Tsuji (1995); Xu et al. (2007).

Experimental top

2-(Dicyclohexylphosphanyl)biphenyl was prepared as described in the literature (Tomori et al., 2000). A solution of PdBr2(PhCN)2 (1 mmol) and 2-(Dicyclohexylphosphanyl)biphenyl (2 mmol) in dry benzene (5 ml) was stirred for 1 day, removal of solvent resulted in a yellow powder that was recrystallized from dichloromethane-petroleum ether solution at room temperature to give the desired product as yellow crystals suitable for single-crystal X-ray diffraction.

Refinement top

H atoms were placed in calculated positions (Csp2—H = 0.93 Å, Csp3—H = 0.97 -0.98 Å) and refined as riding on their carriers with isotropic displacement parameters Uiso(H) = 1.2 times Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: PLATON (Spek, 2003) and SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids of the non-hydrogen atoms drawn at the 30% probability level. Inversion related atoms are labelled with an A.(Symmetry code: 2 - x, 1 - y, 1 - z).
[Figure 2] Fig. 2. Partial view of the crystal packing showing the formation of the chain motif of molecules formed by the intermolecular π···π interactions, extending along the a axis.
Dibromidobis[2-(dicyclohexylphosphanyl)biphenyl-κP]palladium(II) top
Crystal data top
[PdBr2(C24H31P)2]Z = 1
Mr = 967.14F(000) = 496
Triclinic, P1Dx = 1.524 Mg m−3
a = 9.817 (8) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.827 (8) ÅCell parameters from 1503 reflections
c = 11.957 (10) Åθ = 2.4–21.7°
α = 91.582 (11)°µ = 2.45 mm−1
β = 108.822 (10)°T = 291 K
γ = 103.713 (10)°Block, yellow
V = 1053.9 (15) Å30.14 × 0.10 × 0.09 mm
Data collection top
Bruker SMART APEX CCD
diffractometer		3811 independent reflections
Radiation source: fine-focus sealed tube2810 reflections with I > 2σ(I)
graphiteRint = 0.039
φ and ω scansθmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −11→11
Tmin = 0.723, Tmax = 0.803k = −11→11
7316 measured reflectionsl = −14→14
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)] = 0.066Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.180H-atom parameters constrained
S = 1.10 w = 1/[σ2(Fo2) + (0.0609P)2 + 7.3363P]
where P = (Fo2 + 2Fc2)/3
3811 reflections(Δ/σ)max < 0.001
241 parametersΔρmax = 0.71 e Å−3
0 restraintsΔρmin = −1.42 e Å−3
Crystal data top
[PdBr2(C24H31P)2]γ = 103.713 (10)°
Mr = 967.14V = 1053.9 (15) Å3
Triclinic, P1Z = 1
a = 9.817 (8) ÅMo Kα radiation
b = 9.827 (8) ŵ = 2.45 mm−1
c = 11.957 (10) ÅT = 291 K
α = 91.582 (11)°0.14 × 0.10 × 0.09 mm
β = 108.822 (10)°
Data collection top
Bruker SMART APEX CCD
diffractometer		3811 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2810 reflections with I > 2σ(I)
Tmin = 0.723, Tmax = 0.803Rint = 0.039
7316 measured reflectionsθmax = 25.5°
Refinement top
R[F2 > 2σ(F2)] = 0.066H-atom parameters constrained
wR(F2) = 0.180Δρmax = 0.71 e Å−3
S = 1.10Δρmin = −1.42 e Å−3
3811 reflectionsAbsolute structure: ?
241 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
Pd11.00000.50000.50000.0252 (2)
Br10.96825 (13)0.71510 (13)0.59715 (10)0.0612 (4)
P10.8353 (2)0.5540 (2)0.32229 (17)0.0267 (5)
C10.7959 (9)0.4354 (9)0.1852 (7)0.0306 (18)
H10.77030.33920.20600.037*
C20.6642 (9)0.4454 (10)0.0766 (7)0.038 (2)
H2A0.57630.43780.09900.045*
H2B0.68700.53580.04680.045*
C30.6343 (10)0.3264 (10)−0.0199 (8)0.044 (2)
H3A0.60210.23660.00780.053*
H3B0.55460.3355−0.09030.053*
C40.7702 (10)0.3287 (10)−0.0518 (8)0.045 (2)
H4A0.79450.4131−0.08930.054*
H4B0.74880.2479−0.10900.054*
C50.9032 (10)0.3258 (9)0.0551 (8)0.038 (2)
H5A0.99030.33440.03150.046*
H5B0.88430.23690.08790.046*
C60.9318 (9)0.4476 (9)0.1490 (7)0.0362 (19)
H6A1.01670.44560.21800.043*
H6B0.95460.53660.11710.043*
C70.9148 (9)0.7385 (9)0.2981 (7)0.0330 (18)
H70.90690.79810.36160.040*
C80.8334 (10)0.7900 (9)0.1839 (8)0.044 (2)
H8A0.84070.73750.11710.052*
H8B0.72880.77240.17510.052*
C90.8963 (11)0.9454 (10)0.1819 (10)0.056 (3)
H9A0.84710.97230.10480.067*
H9B0.87610.99870.24150.067*
C101.0617 (11)0.9819 (11)0.2059 (10)0.057 (3)
H10A1.08080.94100.13960.068*
H10B1.09931.08350.21240.068*
C111.1426 (10)0.9292 (10)0.3177 (10)0.054 (3)
H11A1.13450.97940.38530.064*
H11B1.24740.94820.32680.064*
C121.0801 (9)0.7721 (9)0.3166 (8)0.039 (2)
H12A1.13220.74190.39140.047*
H12B1.09570.72100.25310.047*
C130.6373 (9)0.2210 (10)0.3590 (8)0.043 (2)
H130.70630.27130.42960.052*
C140.6340 (11)0.0838 (10)0.3309 (9)0.048 (2)
H140.70070.04220.38320.058*
C150.5362 (12)0.0082 (11)0.2291 (10)0.055 (3)
H150.5373−0.08410.21070.066*
C160.4362 (12)0.0670 (11)0.1533 (9)0.056 (3)
H160.36890.01480.08290.067*
C170.4337 (10)0.2035 (10)0.1801 (8)0.047 (2)
H170.36180.24120.12920.056*
C180.5374 (9)0.2858 (9)0.2823 (7)0.0338 (19)
C190.5333 (9)0.4319 (9)0.3139 (7)0.0324 (18)
C200.4018 (9)0.4472 (10)0.3274 (8)0.043 (2)
H200.32190.36780.31140.051*
C210.3852 (10)0.5738 (11)0.3630 (8)0.047 (2)
H210.29670.57950.37330.056*
C220.4983 (11)0.6902 (11)0.3831 (8)0.046 (2)
H220.48710.77700.40560.056*
C230.6325 (10)0.6814 (10)0.3703 (8)0.040 (2)
H230.71040.76260.38620.048*
C240.6521 (9)0.5536 (9)0.3340 (7)0.0306 (18)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.0260 (5)0.0262 (5)0.0248 (5)0.0099 (4)0.0083 (3)0.0043 (3)
Br10.0626 (7)0.0682 (8)0.0511 (7)0.0210 (6)0.0141 (5)0.0072 (5)
P10.0255 (10)0.0281 (11)0.0275 (10)0.0093 (8)0.0084 (8)0.0049 (8)
C10.032 (4)0.035 (5)0.031 (4)0.014 (4)0.014 (3)0.007 (3)
C20.032 (4)0.046 (5)0.036 (5)0.015 (4)0.007 (4)0.004 (4)
C30.043 (5)0.054 (6)0.029 (5)0.009 (4)0.007 (4)0.000 (4)
C40.051 (6)0.045 (6)0.036 (5)−0.001 (4)0.021 (4)−0.005 (4)
C50.047 (5)0.036 (5)0.043 (5)0.015 (4)0.028 (4)0.004 (4)
C60.038 (5)0.038 (5)0.034 (4)0.012 (4)0.013 (4)0.005 (4)
C70.032 (4)0.035 (5)0.036 (5)0.014 (4)0.012 (4)0.007 (4)
C80.040 (5)0.034 (5)0.056 (6)0.010 (4)0.013 (4)0.020 (4)
C90.047 (6)0.039 (6)0.077 (7)0.012 (5)0.013 (5)0.024 (5)
C100.056 (6)0.041 (6)0.072 (7)0.007 (5)0.023 (6)0.019 (5)
C110.033 (5)0.050 (6)0.073 (7)0.002 (4)0.019 (5)0.013 (5)
C120.031 (4)0.037 (5)0.051 (5)0.010 (4)0.015 (4)0.014 (4)
C130.031 (5)0.059 (6)0.039 (5)0.016 (4)0.008 (4)0.010 (4)
C140.052 (6)0.037 (6)0.059 (6)0.020 (5)0.017 (5)0.013 (5)
C150.059 (6)0.032 (6)0.068 (7)0.005 (5)0.021 (6)−0.002 (5)
C160.055 (6)0.046 (6)0.052 (6)−0.005 (5)0.011 (5)−0.004 (5)
C170.037 (5)0.045 (6)0.044 (5)0.001 (4)0.002 (4)0.007 (4)
C180.030 (4)0.031 (5)0.039 (5)0.003 (3)0.015 (4)0.003 (4)
C190.029 (4)0.034 (5)0.035 (4)0.010 (3)0.011 (3)0.004 (4)
C200.027 (4)0.048 (6)0.052 (6)0.010 (4)0.012 (4)0.007 (4)
C210.030 (5)0.067 (7)0.053 (6)0.023 (5)0.018 (4)0.009 (5)
C220.055 (6)0.051 (6)0.051 (6)0.034 (5)0.026 (5)0.012 (5)
C230.038 (5)0.040 (5)0.047 (5)0.015 (4)0.019 (4)0.005 (4)
C240.033 (4)0.034 (5)0.029 (4)0.014 (4)0.012 (3)0.006 (3)
Geometric parameters (Å, °) top
Pd1—P1i2.380 (2)C9—H9B0.9700
Pd1—P12.380 (2)C10—C111.495 (14)
Pd1—Br1i2.515 (2)C10—H10A0.9700
Pd1—Br12.515 (2)C10—H10B0.9700
P1—C241.848 (8)C11—C121.518 (13)
P1—C11.862 (8)C11—H11A0.9700
P1—C71.866 (8)C11—H11B0.9700
C1—C61.510 (11)C12—H12A0.9700
C1—C21.533 (11)C12—H12B0.9700
C1—H10.9800C13—C141.371 (13)
C2—C31.527 (12)C13—C181.398 (12)
C2—H2A0.9700C13—H130.9300
C2—H2B0.9700C14—C151.347 (14)
C3—C41.496 (12)C14—H140.9300
C3—H3A0.9700C15—C161.358 (14)
C3—H3B0.9700C15—H150.9300
C4—C51.511 (12)C16—C171.378 (14)
C4—H4A0.9700C16—H160.9300
C4—H4B0.9700C17—C181.391 (12)
C5—C61.527 (11)C17—H170.9300
C5—H5A0.9700C18—C191.488 (12)
C5—H5B0.9700C19—C201.393 (11)
C6—H6A0.9700C19—C241.410 (11)
C6—H6B0.9700C20—C211.367 (13)
C7—C81.512 (11)C20—H200.9300
C7—C121.518 (11)C21—C221.345 (14)
C7—H70.9800C21—H210.9300
C8—C91.509 (12)C22—C231.396 (12)
C8—H8A0.9700C22—H220.9300
C8—H8B0.9700C23—C241.394 (12)
C9—C101.505 (14)C23—H230.9300
C9—H9A0.9700
P1i—Pd1—P1180.0C10—C9—C8111.9 (8)
P1i—Pd1—Br1i85.15 (7)C10—C9—H9A109.2
P1—Pd1—Br1i94.85 (7)C8—C9—H9A109.2
P1i—Pd1—Br194.85 (7)C10—C9—H9B109.2
P1—Pd1—Br185.15 (7)C8—C9—H9B109.2
Br1i—Pd1—Br1180.000 (2)H9A—C9—H9B107.9
C24—P1—C1106.1 (4)C11—C10—C9111.8 (8)
C24—P1—C7104.9 (4)C11—C10—H10A109.2
C1—P1—C7108.6 (4)C9—C10—H10A109.2
C24—P1—Pd1112.3 (3)C11—C10—H10B109.2
C1—P1—Pd1115.8 (3)C9—C10—H10B109.2
C7—P1—Pd1108.5 (3)H10A—C10—H10B107.9
C6—C1—C2109.2 (7)C10—C11—C12111.6 (8)
C6—C1—P1112.5 (6)C10—C11—H11A109.3
C2—C1—P1116.7 (5)C12—C11—H11A109.3
C6—C1—H1105.9C10—C11—H11B109.3
C2—C1—H1105.9C12—C11—H11B109.3
P1—C1—H1105.9H11A—C11—H11B108.0
C3—C2—C1109.1 (7)C11—C12—C7110.5 (7)
C3—C2—H2A109.9C11—C12—H12A109.6
C1—C2—H2A109.9C7—C12—H12A109.6
C3—C2—H2B109.9C11—C12—H12B109.6
C1—C2—H2B109.9C7—C12—H12B109.6
H2A—C2—H2B108.3H12A—C12—H12B108.1
C4—C3—C2111.7 (7)C14—C13—C18120.4 (9)
C4—C3—H3A109.3C14—C13—H13119.8
C2—C3—H3A109.3C18—C13—H13119.8
C4—C3—H3B109.3C15—C14—C13121.4 (9)
C2—C3—H3B109.3C15—C14—H14119.3
H3A—C3—H3B107.9C13—C14—H14119.3
C3—C4—C5112.5 (7)C14—C15—C16119.8 (10)
C3—C4—H4A109.1C14—C15—H15120.1
C5—C4—H4A109.1C16—C15—H15120.1
C3—C4—H4B109.1C15—C16—C17120.4 (10)
C5—C4—H4B109.1C15—C16—H16119.8
H4A—C4—H4B107.8C17—C16—H16119.8
C4—C5—C6109.5 (7)C16—C17—C18120.9 (9)
C4—C5—H5A109.8C16—C17—H17119.6
C6—C5—H5A109.8C18—C17—H17119.6
C4—C5—H5B109.8C17—C18—C13117.0 (8)
C6—C5—H5B109.8C17—C18—C19121.4 (8)
H5A—C5—H5B108.2C13—C18—C19121.4 (8)
C1—C6—C5110.0 (7)C20—C19—C24118.2 (8)
C1—C6—H6A109.7C20—C19—C18116.4 (7)
C5—C6—H6A109.7C24—C19—C18125.4 (7)
C1—C6—H6B109.7C21—C20—C19122.8 (9)
C5—C6—H6B109.7C21—C20—H20118.6
H6A—C6—H6B108.2C19—C20—H20118.6
C8—C7—C12109.9 (7)C22—C21—C20119.2 (8)
C8—C7—P1117.0 (6)C22—C21—H21120.4
C12—C7—P1113.5 (5)C20—C21—H21120.4
C8—C7—H7105.1C21—C22—C23120.5 (9)
C12—C7—H7105.1C21—C22—H22119.8
P1—C7—H7105.1C23—C22—H22119.8
C9—C8—C7111.9 (8)C24—C23—C22121.3 (9)
C9—C8—H8A109.2C24—C23—H23119.3
C7—C8—H8A109.2C22—C23—H23119.3
C9—C8—H8B109.2C23—C24—C19117.9 (7)
C7—C8—H8B109.2C23—C24—P1117.6 (6)
H8A—C8—H8B107.9C19—C24—P1124.5 (6)
P1i—Pd1—P1—C24103 (35)C9—C10—C11—C1254.5 (12)
Br1i—Pd1—P1—C24120.1 (3)C10—C11—C12—C7−57.0 (11)
Br1—Pd1—P1—C24−59.9 (3)C8—C7—C12—C1157.1 (10)
P1i—Pd1—P1—C1−20 (33)P1—C7—C12—C11−169.7 (7)
Br1i—Pd1—P1—C1−2.1 (3)C18—C13—C14—C150.5 (15)
Br1—Pd1—P1—C1177.9 (3)C13—C14—C15—C16−1.5 (16)
P1i—Pd1—P1—C7−142 (33)C14—C15—C16—C17−0.2 (16)
Br1i—Pd1—P1—C7−124.4 (3)C15—C16—C17—C182.9 (15)
Br1—Pd1—P1—C755.6 (3)C16—C17—C18—C13−3.7 (14)
C24—P1—C1—C6168.1 (6)C16—C17—C18—C19−178.3 (9)
C7—P1—C1—C655.8 (6)C14—C13—C18—C172.1 (13)
Pd1—P1—C1—C6−66.5 (6)C14—C13—C18—C19176.6 (8)
C24—P1—C1—C240.7 (7)C17—C18—C19—C2057.9 (11)
C7—P1—C1—C2−71.6 (7)C13—C18—C19—C20−116.4 (9)
Pd1—P1—C1—C2166.1 (5)C17—C18—C19—C24−123.8 (9)
C6—C1—C2—C359.6 (9)C13—C18—C19—C2461.9 (12)
P1—C1—C2—C3−171.5 (6)C24—C19—C20—C21−2.3 (13)
C1—C2—C3—C4−55.9 (10)C18—C19—C20—C21176.1 (8)
C2—C3—C4—C554.7 (11)C19—C20—C21—C221.9 (14)
C3—C4—C5—C6−55.3 (10)C20—C21—C22—C23−1.4 (14)
C2—C1—C6—C5−61.9 (9)C21—C22—C23—C241.5 (14)
P1—C1—C6—C5166.9 (6)C22—C23—C24—C19−1.8 (12)
C4—C5—C6—C158.9 (9)C22—C23—C24—P1−179.1 (7)
C24—P1—C7—C8−64.7 (7)C20—C19—C24—C232.2 (12)
C1—P1—C7—C848.4 (7)C18—C19—C24—C23−176.0 (8)
Pd1—P1—C7—C8175.1 (6)C20—C19—C24—P1179.2 (6)
C24—P1—C7—C12165.6 (6)C18—C19—C24—P11.0 (12)
C1—P1—C7—C12−81.3 (7)C1—P1—C24—C23−139.6 (6)
Pd1—P1—C7—C1245.3 (7)C7—P1—C24—C23−24.7 (7)
C12—C7—C8—C9−56.0 (10)Pd1—P1—C24—C2393.0 (6)
P1—C7—C8—C9172.6 (7)C1—P1—C24—C1943.4 (8)
C7—C8—C9—C1054.0 (12)C7—P1—C24—C19158.3 (7)
C8—C9—C10—C11−52.8 (13)Pd1—P1—C24—C19−84.1 (7)
Symmetry codes: (i) −x+2, −y+1, −z+1.
Acknowledgements top

This work was supported by the Doctoral Foundation of Luoyang Normal University, People's Republic of China.

references
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