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Acta Cryst. (2007). E63, m2558    [ doi:10.1107/S160053680704528X ]

Bis(tetraphenylphosphonium) di-[mu]-iodido-bis[diiodidopalladate(II)]

F. Mulligan, G. S. Nichol and S. K. Hurst

Abstract top

The title compound, (PPh4)2[Pd2I6], was obtained unintentionally as the product of an attempted synthesis of a tripalladium sandwich complex. The molecular dimensions are unexceptional and the Pd...Pd distance, at 3.8183 (12) Å, is much too long for any Pd-Pd interaction. Pd has a typical square-planar coordination geometry and the centrosymmetric anion is essentially planar.

Comment top

The title compound, (I), was obtained unintentionally as the product of an attempted synthesis of a tripalladium sandwich complex. The [Pd2I6]2− ion lies on an inversion centre and thus the asymmetric unit is one-half of the complete chemical formula.

Both palladium centres have typical d8 square-planar geometry and are bridged by two iodide ligands, with four terminal iodide ligands completing this discrete species. A search of the Cambridge Structural Database (Version 5.28 with two updates; Allen, 2002) shows that there are only 8 reported crystallographic examples of this unit. Two tetraphenylphosphonium cations balance the 2- charge. Molecular dimensions are unexceptional and the Pd···Pd distance, at 3.8183 (12) Å, is much too long for any Pd—Pd interaction.

The crystal packing consists mostly of coulombic and London forces, with the exception that the tetraphenylphosphonium cations show the typical phenyl embrace interactions usually encountered with this type of species.

Related literature top

The PPh3Me+ salt has also been reported (Tonde et al., 2005). For other examples of [Pd2I6]2− see Chan et al. (1996), Evans et al. (2002), Maassarani et al. (1987), Neve et al. (2000) and Neve & Crispini (2003). For the Cambridge Strcutural Database, see Allen (2002).

Experimental top

200 mg of Pd2(dba)3 (dba = dibenzylideneacetone) was stirred with 46 mg of C7H7·BF4 and 445 mg of PPh4I in 30 ml of CH2Cl2 for 30 minutes at room temperature. The solvent was removed under vacuum and the residue recrystallized by slow evaporation of an acetonitrile solution. Yield = 12%. 1H NMR: (400 MHz, CDCl3): δ (p.p.m.) = 7.05 – 8.05 (40 H, m, Ph). 31P NMR: (400 MHz, CDCl3): δ (p.p.m.) = 24.2.

Refinement top

All hydrogen atoms were initially located in a difference map and then refined using a riding model with Uiso(H)=1.2Ueq(C). The C–H distances were constrained to be 0.95 Å.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 2001) and local programs.

Figures top
[Figure 1] Fig. 1. Twice the asymmetric unit of (I) with displacement ellipsoids at the 50% probability level and hydrogen atoms shown as small spheres. Symmetry operation a: −x + 1,-y,-z + 1.
Bis(tetraphenylphosphonium) di-µ-iodidobis[diiodidodipalladate(II)] top
Crystal data top
(C24H20P)2[Pd2I6]F000 = 1536
Mr = 1652.94Dx = 2.206 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 5989 reflections
a = 12.8951 (11) Åθ = 2.4–27.3º
b = 14.4427 (13) ŵ = 4.54 mm−1
c = 13.9409 (12) ÅT = 150 (2) K
β = 106.613 (1)ºPlate, dark purple
V = 2488.0 (4) Å30.39 × 0.24 × 0.05 mm
Z = 2
Data collection top
Bruker SMART 1000 CCD
diffractometer		4154 independent reflections
Radiation source: sealed tube2914 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.040
T = 150(2) Kθmax = 25.0º
thin–slice ω scansθmin = 1.9º
Absorption correction: Gaussian
(SADABS; Sheldrick, 2007)		h = −15→15
Tmin = 0.268, Tmax = 0.805k = −17→17
15011 measured reflectionsl = −16→16
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0253P)2 + 19.5288P]
where P = (Fo2 + 2Fc2)/3
S = 1.14(Δ/σ)max = 0.001
4154 reflectionsΔρmax = 1.19 e Å−3
262 parametersΔρmin = −0.98 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C24H20P)2[Pd2I6]V = 2488.0 (4) Å3
Mr = 1652.94Z = 2
Monoclinic, P21/nMo Kα
a = 12.8951 (11) ŵ = 4.54 mm−1
b = 14.4427 (13) ÅT = 150 (2) K
c = 13.9409 (12) Å0.39 × 0.24 × 0.05 mm
β = 106.613 (1)º
Data collection top
Bruker SMART 1000 CCD
diffractometer		4154 independent reflections
Absorption correction: Gaussian
(SADABS; Sheldrick, 2007)		2914 reflections with I > 2σ(I)
Tmin = 0.268, Tmax = 0.805Rint = 0.040
15011 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.101  w = 1/[σ2(Fo2) + (0.0253P)2 + 19.5288P]
where P = (Fo2 + 2Fc2)/3
S = 1.14Δρmax = 1.19 e Å−3
4154 reflectionsΔρmin = −0.98 e Å−3
262 parameters
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
I10.59662 (4)0.06678 (3)0.59089 (4)0.02764 (15)
I20.58538 (5)−0.07752 (5)0.24562 (5)0.0469 (2)
I30.78898 (4)0.05801 (4)0.43871 (4)0.03281 (16)
Pd0.59643 (5)−0.00576 (4)0.41867 (4)0.02353 (16)
P0.81570 (15)0.11432 (13)0.04585 (14)0.0193 (4)
C10.7167 (6)0.1895 (5)0.0730 (6)0.0223 (17)
C20.6358 (6)0.2255 (5)−0.0063 (7)0.0301 (19)
H20.63210.2096−0.07330.036*
C30.5600 (7)0.2853 (6)0.0138 (7)0.037 (2)
H30.50360.3098−0.03980.044*
C40.5662 (7)0.3091 (6)0.1103 (7)0.036 (2)
H40.51490.35100.12310.043*
C50.6462 (8)0.2728 (7)0.1890 (8)0.047 (3)
H50.65000.28920.25590.056*
C60.7203 (7)0.2128 (6)0.1700 (6)0.037 (2)
H60.77490.18700.22430.044*
C70.7644 (6)−0.0016 (5)0.0212 (5)0.0220 (17)
C80.8366 (7)−0.0763 (5)0.0443 (6)0.0265 (18)
H80.9119−0.06640.07300.032*
C90.7950 (7)−0.1646 (5)0.0240 (6)0.032 (2)
H90.8425−0.21620.04060.038*
C100.6872 (7)−0.1793 (6)−0.0193 (6)0.031 (2)
H100.6604−0.2406−0.03360.037*
C110.6170 (7)−0.1048 (6)−0.0423 (6)0.034 (2)
H110.5420−0.1150−0.07260.040*
C120.6551 (6)−0.0169 (5)−0.0216 (6)0.0264 (18)
H120.60650.0340−0.03660.032*
C130.9359 (6)0.1100 (5)0.1492 (5)0.0220 (16)
C141.0305 (7)0.1553 (6)0.1453 (6)0.0313 (19)
H141.03160.18960.08750.038*
C151.1226 (7)0.1500 (6)0.2262 (6)0.032 (2)
H151.18740.17940.22290.039*
C161.1208 (6)0.1026 (5)0.3110 (6)0.0275 (18)
H161.18380.09970.36660.033*
C171.0267 (7)0.0591 (6)0.3149 (6)0.0299 (19)
H171.02580.02640.37380.036*
C180.9347 (7)0.0619 (6)0.2357 (6)0.0297 (19)
H180.87080.03140.23970.036*
C190.8461 (6)0.1608 (5)−0.0624 (6)0.0218 (16)
C200.8435 (6)0.1058 (5)−0.1451 (6)0.0251 (17)
H200.82250.0426−0.14630.030*
C210.8716 (6)0.1431 (5)−0.2253 (6)0.0275 (18)
H210.86930.1061−0.28220.033*
C220.9033 (6)0.2357 (5)−0.2223 (6)0.0245 (17)
H220.92380.2614−0.27690.029*
C230.9050 (6)0.2901 (5)−0.1407 (6)0.0250 (17)
H230.92640.3532−0.13960.030*
C240.8760 (6)0.2540 (5)−0.0612 (6)0.0255 (18)
H240.87630.2920−0.00550.031*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.0230 (3)0.0257 (3)0.0314 (3)−0.0031 (2)0.0033 (2)−0.0049 (2)
I20.0438 (4)0.0617 (4)0.0314 (3)0.0086 (3)0.0049 (3)−0.0113 (3)
I30.0272 (3)0.0357 (3)0.0363 (3)−0.0050 (2)0.0104 (2)0.0038 (3)
Pd0.0214 (3)0.0206 (3)0.0261 (3)0.0017 (2)0.0028 (3)0.0014 (3)
P0.0183 (10)0.0181 (9)0.0213 (10)−0.0010 (8)0.0054 (8)−0.0025 (8)
C10.017 (4)0.022 (4)0.030 (4)−0.004 (3)0.011 (3)−0.003 (3)
C20.031 (5)0.026 (4)0.036 (5)0.003 (4)0.014 (4)0.005 (4)
C30.032 (5)0.033 (5)0.051 (6)0.016 (4)0.022 (4)0.025 (5)
C40.040 (5)0.023 (4)0.057 (6)0.003 (4)0.032 (5)−0.002 (4)
C50.044 (6)0.053 (6)0.050 (6)0.000 (5)0.023 (5)−0.025 (5)
C60.039 (5)0.042 (5)0.029 (5)0.007 (4)0.009 (4)−0.003 (4)
C70.029 (4)0.017 (4)0.019 (4)−0.003 (3)0.005 (3)0.003 (3)
C80.026 (4)0.022 (4)0.029 (4)−0.001 (3)0.005 (4)−0.006 (4)
C90.045 (5)0.022 (4)0.031 (5)0.007 (4)0.013 (4)0.000 (4)
C100.034 (5)0.022 (4)0.033 (5)−0.009 (4)0.002 (4)−0.004 (4)
C110.028 (5)0.028 (4)0.038 (5)−0.008 (4)−0.002 (4)0.000 (4)
C120.014 (4)0.023 (4)0.037 (5)−0.003 (3)−0.001 (3)−0.002 (4)
C130.021 (4)0.023 (4)0.021 (4)−0.004 (3)0.005 (3)−0.006 (3)
C140.031 (5)0.027 (4)0.034 (5)−0.001 (4)0.007 (4)0.005 (4)
C150.023 (4)0.038 (5)0.034 (5)−0.010 (4)0.007 (4)−0.007 (4)
C160.015 (4)0.031 (4)0.032 (4)0.004 (3)−0.002 (3)−0.007 (4)
C170.038 (5)0.028 (4)0.023 (4)0.005 (4)0.008 (4)−0.001 (4)
C180.029 (5)0.034 (5)0.027 (4)−0.005 (4)0.011 (4)−0.010 (4)
C190.020 (4)0.023 (4)0.023 (4)0.003 (3)0.009 (3)0.000 (3)
C200.022 (4)0.020 (4)0.031 (4)−0.001 (3)0.004 (3)0.000 (4)
C210.029 (5)0.029 (4)0.024 (4)0.004 (4)0.007 (4)0.001 (4)
C220.022 (4)0.025 (4)0.027 (4)0.003 (3)0.007 (3)0.010 (4)
C230.025 (4)0.023 (4)0.026 (4)0.000 (3)0.007 (3)0.003 (4)
C240.025 (4)0.021 (4)0.028 (4)−0.003 (3)0.004 (4)−0.008 (4)
Geometric parameters (Å, °) top
I1—Pd2.6188 (8)C10—C111.384 (11)
I1—Pdi2.6081 (8)C11—H110.950
I2—Pd2.5920 (9)C11—C121.362 (11)
I3—Pd2.5874 (8)C12—H120.950
Pd—I1i2.6080 (8)C13—C141.399 (11)
P—C11.796 (8)C13—C181.396 (11)
P—C71.797 (7)C14—H140.950
P—C131.790 (8)C14—C151.387 (11)
P—C191.795 (8)C15—H150.950
C1—C21.386 (11)C15—C161.372 (11)
C1—C61.382 (11)C16—H160.950
C2—H20.950C16—C171.381 (11)
C2—C31.392 (11)C17—H170.950
C3—H30.950C17—C181.371 (11)
C3—C41.369 (12)C18—H180.950
C4—H40.950C19—C201.392 (10)
C4—C51.377 (13)C19—C241.399 (10)
C5—H50.950C20—H200.950
C5—C61.371 (12)C20—C211.379 (11)
C6—H60.950C21—H210.950
C7—C81.400 (10)C21—C221.396 (11)
C7—C121.382 (10)C22—H220.950
C8—H80.950C22—C231.378 (11)
C8—C91.382 (11)C23—H230.950
C9—H90.950C23—C241.371 (11)
C9—C101.365 (11)C24—H240.950
C10—H100.950
Pd—I1—Pdi93.86 (2)C10—C11—H11119.9
I1—Pd—I1i86.14 (2)C10—C11—C12120.2 (8)
I1—Pd—I2177.03 (3)H11—C11—C12119.9
I1i—Pd—I291.12 (3)C7—C12—C11120.1 (7)
I1—Pd—I390.53 (3)C7—C12—H12119.9
I1i—Pd—I3176.65 (3)C11—C12—H12119.9
I2—Pd—I392.21 (3)P—C13—C14121.1 (6)
C1—P—C7111.0 (3)P—C13—C18119.5 (6)
C1—P—C13110.8 (3)C14—C13—C18119.4 (7)
C1—P—C19106.9 (3)C13—C14—H14120.1
C7—P—C13108.0 (3)C13—C14—C15119.8 (8)
C7—P—C19110.1 (3)H14—C14—C15120.1
C13—P—C19110.1 (3)C14—C15—H15119.8
P—C1—C2118.5 (6)C14—C15—C16120.4 (8)
P—C1—C6121.8 (6)H15—C15—C16119.8
C2—C1—C6119.7 (7)C15—C16—H16120.2
C1—C2—H2120.5C15—C16—C17119.5 (7)
C1—C2—C3119.0 (8)H16—C16—C17120.2
H2—C2—C3120.5C16—C17—H17119.2
C2—C3—H3119.8C16—C17—C18121.5 (8)
C2—C3—C4120.5 (8)H17—C17—C18119.2
H3—C3—C4119.8C13—C18—C17119.3 (8)
C3—C4—H4119.8C13—C18—H18120.4
C3—C4—C5120.5 (8)C17—C18—H18120.4
H4—C4—C5119.8P—C19—C20121.6 (6)
C4—C5—H5120.3P—C19—C24118.4 (6)
C4—C5—C6119.5 (9)C20—C19—C24120.0 (7)
H5—C5—C6120.3C19—C20—H20120.1
C1—C6—C5120.9 (9)C19—C20—C21119.9 (7)
C1—C6—H6119.6H20—C20—C21120.1
C5—C6—H6119.6C20—C21—H21120.2
P—C7—C8119.3 (6)C20—C21—C22119.6 (7)
P—C7—C12120.4 (6)H21—C21—C22120.2
C8—C7—C12120.3 (7)C21—C22—H22119.8
C7—C8—H8120.9C21—C22—C23120.4 (7)
C7—C8—C9118.1 (7)H22—C22—C23119.8
H8—C8—C9120.9C22—C23—H23119.8
C8—C9—H9119.3C22—C23—C24120.4 (7)
C8—C9—C10121.4 (8)H23—C23—C24119.8
H9—C9—C10119.3C19—C24—C23119.7 (7)
C9—C10—H10120.1C19—C24—H24120.2
C9—C10—C11119.9 (7)C23—C24—H24120.2
H10—C10—C11120.1
Pdi—I1—Pd—I1i0.0C8—C7—C12—C11−0.5 (12)
Pdi—I1—Pd—I223.0 (6)C1—P—C13—C14−106.1 (7)
Pdi—I1—Pd—I3−179.59 (3)C1—P—C13—C1872.9 (7)
C7—P—C1—C2−81.2 (7)C7—P—C13—C14132.1 (7)
C7—P—C1—C699.7 (7)C7—P—C13—C18−48.9 (7)
C13—P—C1—C2158.9 (6)C19—P—C13—C1411.9 (8)
C13—P—C1—C6−20.3 (8)C19—P—C13—C18−169.1 (6)
C19—P—C1—C239.0 (7)P—C13—C14—C15−179.4 (6)
C19—P—C1—C6−140.2 (7)C18—C13—C14—C151.6 (12)
P—C1—C2—C3−178.7 (6)C13—C14—C15—C16−1.6 (12)
C6—C1—C2—C30.5 (12)C14—C15—C16—C170.8 (12)
C1—C2—C3—C40.8 (12)C15—C16—C17—C180.2 (12)
C2—C3—C4—C5−1.3 (13)C16—C17—C18—C13−0.2 (12)
C3—C4—C5—C60.4 (14)P—C13—C18—C17−179.7 (6)
C4—C5—C6—C11.0 (14)C14—C13—C18—C17−0.7 (12)
P—C1—C6—C5177.7 (7)C1—P—C19—C20−129.3 (6)
C2—C1—C6—C5−1.4 (13)C1—P—C19—C2452.6 (7)
C1—P—C7—C8−150.3 (6)C7—P—C19—C20−8.7 (7)
C1—P—C7—C1230.7 (7)C7—P—C19—C24173.3 (6)
C13—P—C7—C8−28.6 (7)C13—P—C19—C20110.2 (6)
C13—P—C7—C12152.4 (6)C13—P—C19—C24−67.8 (7)
C19—P—C7—C891.6 (7)P—C19—C20—C21−177.4 (6)
C19—P—C7—C12−87.4 (7)C24—C19—C20—C210.6 (11)
P—C7—C8—C9−179.7 (6)C19—C20—C21—C220.6 (11)
C12—C7—C8—C9−0.7 (12)C20—C21—C22—C23−1.1 (11)
C7—C8—C9—C101.5 (12)C21—C22—C23—C240.3 (11)
C8—C9—C10—C11−1.0 (13)C22—C23—C24—C191.0 (11)
C9—C10—C11—C12−0.2 (13)P—C19—C24—C23176.7 (6)
C10—C11—C12—C70.9 (13)C20—C19—C24—C23−1.4 (11)
P—C7—C12—C11178.5 (7)
Symmetry codes: (i) −x+1, −y, −z+1.
Acknowledgements top

The work described in this paper was supported by the Northern Arizona University (NAU) Intramural Grant Program, the NAU College of Engineering and Natural Science start-up fund and the SABRE GBI program. The X-ray diffractometer was purchased with NSF grant CHEM960374.

references
References top

Allen, F. H. (2002). Acta Cryst. B58, 380–388.

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Chan, S., Lee, S.-M., Lin, A. & Wong, W.-T. (1996). J. Organomet. Chem. 510, 219–231.

Evans, J., O'Neill, L., Kambhampati, V. L., Rayner, G., Turin, S., Genge, A., Dent, A. J. & Neisius, T. (2002). Dalton Trans. pp. 2207–2212.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Maassarani, F., Pfeffer, M. & Le Borgne, G. (1987). Organometallics, 6, 2043–2053.

Neve, F., Crispini, A. & Francescangeli, O. (2000). Inorg. Chem. 39, 1187–1194.

Neve, F. & Crispini, A. (2003). CrystEngComm, 5, 265–268.

Sheldrick, G. M. (2001). SHELXTL. Version 6. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (2007). SADABS. University of Göttingen, Germany.

Tonde, S. S., Kelkar, A. A., Bhadbhade, M. M. & Chaudhari, R. V. (2005). J. Organomet. Chem. 690, 1677–1681.