Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680704528X/cf2142sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680704528X/cf2142Isup2.hkl |
CCDC reference: 663615
Key indicators
- Single-crystal X-ray study
- T = 150 K
- Mean (C-C) = 0.012 Å
- R factor = 0.032
- wR factor = 0.101
- Data-to-parameter ratio = 15.9
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95
Alert level C REFLT03_ALERT_3_C Reflection count < 95% complete From the CIF: _diffrn_reflns_theta_max 25.00 From the CIF: _diffrn_reflns_theta_full 25.00 From the CIF: _reflns_number_total 4154 TEST2: Reflns within _diffrn_reflns_theta_max Count of symmetry unique reflns 4380 Completeness (_total/calc) 94.84% PLAT022_ALERT_3_C Ratio Unique / Expected Reflections too Low .... 0.95 PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ .... ? PLAT045_ALERT_1_C Calculated and Reported Z Differ by ............ 2.00 Ratio PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 12 PLAT710_ALERT_4_C Delete 1-2-3 or 2-3-4 Linear Torsion Angle ... # 2 PD -I1 -PD -I2 23.00 0.60 3.656 1.555 1.555 1.555
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Pd (2) 2.08
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 1 ALERT type 5 Informative message, check
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.
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.
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.
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).
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.
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. |
(C24H20P)2[Pd2I6] | F(000) = 1536 |
Mr = 1652.94 | Dx = 2.206 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 5989 reflections |
a = 12.8951 (11) Å | θ = 2.4–27.3° |
b = 14.4427 (13) Å | µ = 4.54 mm−1 |
c = 13.9409 (12) Å | T = 150 K |
β = 106.613 (1)° | Plate, dark purple |
V = 2488.0 (4) Å3 | 0.39 × 0.24 × 0.05 mm |
Z = 2 |
Bruker SMART 1000 CCD diffractometer | 4154 independent reflections |
Radiation source: sealed tube | 2914 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.040 |
thin–slice ω scans | θmax = 25.0°, θmin = 1.9° |
Absorption correction: gaussian (SADABS; Sheldrick, 2007) | h = −15→15 |
Tmin = 0.268, Tmax = 0.805 | k = −17→17 |
15011 measured reflections | l = −16→16 |
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)] = 0.032 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0253P)2 + 19.5288P] where P = (Fo2 + 2Fc2)/3 |
4154 reflections | (Δ/σ)max = 0.001 |
262 parameters | Δρmax = 1.19 e Å−3 |
0 restraints | Δρmin = −0.98 e Å−3 |
(C24H20P)2[Pd2I6] | V = 2488.0 (4) Å3 |
Mr = 1652.94 | Z = 2 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.8951 (11) Å | µ = 4.54 mm−1 |
b = 14.4427 (13) Å | T = 150 K |
c = 13.9409 (12) Å | 0.39 × 0.24 × 0.05 mm |
β = 106.613 (1)° |
Bruker SMART 1000 CCD diffractometer | 4154 independent reflections |
Absorption correction: gaussian (SADABS; Sheldrick, 2007) | 2914 reflections with I > 2σ(I) |
Tmin = 0.268, Tmax = 0.805 | Rint = 0.040 |
15011 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 0 restraints |
wR(F2) = 0.101 | H-atom parameters constrained |
S = 1.14 | w = 1/[σ2(Fo2) + (0.0253P)2 + 19.5288P] where P = (Fo2 + 2Fc2)/3 |
4154 reflections | Δρmax = 1.19 e Å−3 |
262 parameters | Δρmin = −0.98 e Å−3 |
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 | ||
I1 | 0.59662 (4) | 0.06678 (3) | 0.59089 (4) | 0.02764 (15) | |
I2 | 0.58538 (5) | −0.07752 (5) | 0.24562 (5) | 0.0469 (2) | |
I3 | 0.78898 (4) | 0.05801 (4) | 0.43871 (4) | 0.03281 (16) | |
Pd | 0.59643 (5) | −0.00576 (4) | 0.41867 (4) | 0.02353 (16) | |
P | 0.81570 (15) | 0.11432 (13) | 0.04585 (14) | 0.0193 (4) | |
C1 | 0.7167 (6) | 0.1895 (5) | 0.0730 (6) | 0.0223 (17) | |
C2 | 0.6358 (6) | 0.2255 (5) | −0.0063 (7) | 0.0301 (19) | |
H2 | 0.6321 | 0.2096 | −0.0733 | 0.036* | |
C3 | 0.5600 (7) | 0.2853 (6) | 0.0138 (7) | 0.037 (2) | |
H3 | 0.5036 | 0.3098 | −0.0398 | 0.044* | |
C4 | 0.5662 (7) | 0.3091 (6) | 0.1103 (7) | 0.036 (2) | |
H4 | 0.5149 | 0.3510 | 0.1231 | 0.043* | |
C5 | 0.6462 (8) | 0.2728 (7) | 0.1890 (8) | 0.047 (3) | |
H5 | 0.6500 | 0.2892 | 0.2559 | 0.056* | |
C6 | 0.7203 (7) | 0.2128 (6) | 0.1700 (6) | 0.037 (2) | |
H6 | 0.7749 | 0.1870 | 0.2243 | 0.044* | |
C7 | 0.7644 (6) | −0.0016 (5) | 0.0212 (5) | 0.0220 (17) | |
C8 | 0.8366 (7) | −0.0763 (5) | 0.0443 (6) | 0.0265 (18) | |
H8 | 0.9119 | −0.0664 | 0.0730 | 0.032* | |
C9 | 0.7950 (7) | −0.1646 (5) | 0.0240 (6) | 0.032 (2) | |
H9 | 0.8425 | −0.2162 | 0.0406 | 0.038* | |
C10 | 0.6872 (7) | −0.1793 (6) | −0.0193 (6) | 0.031 (2) | |
H10 | 0.6604 | −0.2406 | −0.0336 | 0.037* | |
C11 | 0.6170 (7) | −0.1048 (6) | −0.0423 (6) | 0.034 (2) | |
H11 | 0.5420 | −0.1150 | −0.0726 | 0.040* | |
C12 | 0.6551 (6) | −0.0169 (5) | −0.0216 (6) | 0.0264 (18) | |
H12 | 0.6065 | 0.0340 | −0.0366 | 0.032* | |
C13 | 0.9359 (6) | 0.1100 (5) | 0.1492 (5) | 0.0220 (16) | |
C14 | 1.0305 (7) | 0.1553 (6) | 0.1453 (6) | 0.0313 (19) | |
H14 | 1.0316 | 0.1896 | 0.0875 | 0.038* | |
C15 | 1.1226 (7) | 0.1500 (6) | 0.2262 (6) | 0.032 (2) | |
H15 | 1.1874 | 0.1794 | 0.2229 | 0.039* | |
C16 | 1.1208 (6) | 0.1026 (5) | 0.3110 (6) | 0.0275 (18) | |
H16 | 1.1838 | 0.0997 | 0.3666 | 0.033* | |
C17 | 1.0267 (7) | 0.0591 (6) | 0.3149 (6) | 0.0299 (19) | |
H17 | 1.0258 | 0.0264 | 0.3738 | 0.036* | |
C18 | 0.9347 (7) | 0.0619 (6) | 0.2357 (6) | 0.0297 (19) | |
H18 | 0.8708 | 0.0314 | 0.2397 | 0.036* | |
C19 | 0.8461 (6) | 0.1608 (5) | −0.0624 (6) | 0.0218 (16) | |
C20 | 0.8435 (6) | 0.1058 (5) | −0.1451 (6) | 0.0251 (17) | |
H20 | 0.8225 | 0.0426 | −0.1463 | 0.030* | |
C21 | 0.8716 (6) | 0.1431 (5) | −0.2253 (6) | 0.0275 (18) | |
H21 | 0.8693 | 0.1061 | −0.2822 | 0.033* | |
C22 | 0.9033 (6) | 0.2357 (5) | −0.2223 (6) | 0.0245 (17) | |
H22 | 0.9238 | 0.2614 | −0.2769 | 0.029* | |
C23 | 0.9050 (6) | 0.2901 (5) | −0.1407 (6) | 0.0250 (17) | |
H23 | 0.9264 | 0.3532 | −0.1396 | 0.030* | |
C24 | 0.8760 (6) | 0.2540 (5) | −0.0612 (6) | 0.0255 (18) | |
H24 | 0.8763 | 0.2920 | −0.0055 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0230 (3) | 0.0257 (3) | 0.0314 (3) | −0.0031 (2) | 0.0033 (2) | −0.0049 (2) |
I2 | 0.0438 (4) | 0.0617 (4) | 0.0314 (3) | 0.0086 (3) | 0.0049 (3) | −0.0113 (3) |
I3 | 0.0272 (3) | 0.0357 (3) | 0.0363 (3) | −0.0050 (2) | 0.0104 (2) | 0.0038 (3) |
Pd | 0.0214 (3) | 0.0206 (3) | 0.0261 (3) | 0.0017 (2) | 0.0028 (3) | 0.0014 (3) |
P | 0.0183 (10) | 0.0181 (9) | 0.0213 (10) | −0.0010 (8) | 0.0054 (8) | −0.0025 (8) |
C1 | 0.017 (4) | 0.022 (4) | 0.030 (4) | −0.004 (3) | 0.011 (3) | −0.003 (3) |
C2 | 0.031 (5) | 0.026 (4) | 0.036 (5) | 0.003 (4) | 0.014 (4) | 0.005 (4) |
C3 | 0.032 (5) | 0.033 (5) | 0.051 (6) | 0.016 (4) | 0.022 (4) | 0.025 (5) |
C4 | 0.040 (5) | 0.023 (4) | 0.057 (6) | 0.003 (4) | 0.032 (5) | −0.002 (4) |
C5 | 0.044 (6) | 0.053 (6) | 0.050 (6) | 0.000 (5) | 0.023 (5) | −0.025 (5) |
C6 | 0.039 (5) | 0.042 (5) | 0.029 (5) | 0.007 (4) | 0.009 (4) | −0.003 (4) |
C7 | 0.029 (4) | 0.017 (4) | 0.019 (4) | −0.003 (3) | 0.005 (3) | 0.003 (3) |
C8 | 0.026 (4) | 0.022 (4) | 0.029 (4) | −0.001 (3) | 0.005 (4) | −0.006 (4) |
C9 | 0.045 (5) | 0.022 (4) | 0.031 (5) | 0.007 (4) | 0.013 (4) | 0.000 (4) |
C10 | 0.034 (5) | 0.022 (4) | 0.033 (5) | −0.009 (4) | 0.002 (4) | −0.004 (4) |
C11 | 0.028 (5) | 0.028 (4) | 0.038 (5) | −0.008 (4) | −0.002 (4) | 0.000 (4) |
C12 | 0.014 (4) | 0.023 (4) | 0.037 (5) | −0.003 (3) | −0.001 (3) | −0.002 (4) |
C13 | 0.021 (4) | 0.023 (4) | 0.021 (4) | −0.004 (3) | 0.005 (3) | −0.006 (3) |
C14 | 0.031 (5) | 0.027 (4) | 0.034 (5) | −0.001 (4) | 0.007 (4) | 0.005 (4) |
C15 | 0.023 (4) | 0.038 (5) | 0.034 (5) | −0.010 (4) | 0.007 (4) | −0.007 (4) |
C16 | 0.015 (4) | 0.031 (4) | 0.032 (4) | 0.004 (3) | −0.002 (3) | −0.007 (4) |
C17 | 0.038 (5) | 0.028 (4) | 0.023 (4) | 0.005 (4) | 0.008 (4) | −0.001 (4) |
C18 | 0.029 (5) | 0.034 (5) | 0.027 (4) | −0.005 (4) | 0.011 (4) | −0.010 (4) |
C19 | 0.020 (4) | 0.023 (4) | 0.023 (4) | 0.003 (3) | 0.009 (3) | 0.000 (3) |
C20 | 0.022 (4) | 0.020 (4) | 0.031 (4) | −0.001 (3) | 0.004 (3) | 0.000 (4) |
C21 | 0.029 (5) | 0.029 (4) | 0.024 (4) | 0.004 (4) | 0.007 (4) | 0.001 (4) |
C22 | 0.022 (4) | 0.025 (4) | 0.027 (4) | 0.003 (3) | 0.007 (3) | 0.010 (4) |
C23 | 0.025 (4) | 0.023 (4) | 0.026 (4) | 0.000 (3) | 0.007 (3) | 0.003 (4) |
C24 | 0.025 (4) | 0.021 (4) | 0.028 (4) | −0.003 (3) | 0.004 (4) | −0.008 (4) |
I1—Pd | 2.6188 (8) | C10—C11 | 1.384 (11) |
I1—Pdi | 2.6081 (8) | C11—H11 | 0.950 |
I2—Pd | 2.5920 (9) | C11—C12 | 1.362 (11) |
I3—Pd | 2.5874 (8) | C12—H12 | 0.950 |
Pd—I1i | 2.6080 (8) | C13—C14 | 1.399 (11) |
P—C1 | 1.796 (8) | C13—C18 | 1.396 (11) |
P—C7 | 1.797 (7) | C14—H14 | 0.950 |
P—C13 | 1.790 (8) | C14—C15 | 1.387 (11) |
P—C19 | 1.795 (8) | C15—H15 | 0.950 |
C1—C2 | 1.386 (11) | C15—C16 | 1.372 (11) |
C1—C6 | 1.382 (11) | C16—H16 | 0.950 |
C2—H2 | 0.950 | C16—C17 | 1.381 (11) |
C2—C3 | 1.392 (11) | C17—H17 | 0.950 |
C3—H3 | 0.950 | C17—C18 | 1.371 (11) |
C3—C4 | 1.369 (12) | C18—H18 | 0.950 |
C4—H4 | 0.950 | C19—C20 | 1.392 (10) |
C4—C5 | 1.377 (13) | C19—C24 | 1.399 (10) |
C5—H5 | 0.950 | C20—H20 | 0.950 |
C5—C6 | 1.371 (12) | C20—C21 | 1.379 (11) |
C6—H6 | 0.950 | C21—H21 | 0.950 |
C7—C8 | 1.400 (10) | C21—C22 | 1.396 (11) |
C7—C12 | 1.382 (10) | C22—H22 | 0.950 |
C8—H8 | 0.950 | C22—C23 | 1.378 (11) |
C8—C9 | 1.382 (11) | C23—H23 | 0.950 |
C9—H9 | 0.950 | C23—C24 | 1.371 (11) |
C9—C10 | 1.365 (11) | C24—H24 | 0.950 |
C10—H10 | 0.950 | ||
Pd—I1—Pdi | 93.86 (2) | C10—C11—H11 | 119.9 |
I1—Pd—I1i | 86.14 (2) | C10—C11—C12 | 120.2 (8) |
I1—Pd—I2 | 177.03 (3) | H11—C11—C12 | 119.9 |
I1i—Pd—I2 | 91.12 (3) | C7—C12—C11 | 120.1 (7) |
I1—Pd—I3 | 90.53 (3) | C7—C12—H12 | 119.9 |
I1i—Pd—I3 | 176.65 (3) | C11—C12—H12 | 119.9 |
I2—Pd—I3 | 92.21 (3) | P—C13—C14 | 121.1 (6) |
C1—P—C7 | 111.0 (3) | P—C13—C18 | 119.5 (6) |
C1—P—C13 | 110.8 (3) | C14—C13—C18 | 119.4 (7) |
C1—P—C19 | 106.9 (3) | C13—C14—H14 | 120.1 |
C7—P—C13 | 108.0 (3) | C13—C14—C15 | 119.8 (8) |
C7—P—C19 | 110.1 (3) | H14—C14—C15 | 120.1 |
C13—P—C19 | 110.1 (3) | C14—C15—H15 | 119.8 |
P—C1—C2 | 118.5 (6) | C14—C15—C16 | 120.4 (8) |
P—C1—C6 | 121.8 (6) | H15—C15—C16 | 119.8 |
C2—C1—C6 | 119.7 (7) | C15—C16—H16 | 120.2 |
C1—C2—H2 | 120.5 | C15—C16—C17 | 119.5 (7) |
C1—C2—C3 | 119.0 (8) | H16—C16—C17 | 120.2 |
H2—C2—C3 | 120.5 | C16—C17—H17 | 119.2 |
C2—C3—H3 | 119.8 | C16—C17—C18 | 121.5 (8) |
C2—C3—C4 | 120.5 (8) | H17—C17—C18 | 119.2 |
H3—C3—C4 | 119.8 | C13—C18—C17 | 119.3 (8) |
C3—C4—H4 | 119.8 | C13—C18—H18 | 120.4 |
C3—C4—C5 | 120.5 (8) | C17—C18—H18 | 120.4 |
H4—C4—C5 | 119.8 | P—C19—C20 | 121.6 (6) |
C4—C5—H5 | 120.3 | P—C19—C24 | 118.4 (6) |
C4—C5—C6 | 119.5 (9) | C20—C19—C24 | 120.0 (7) |
H5—C5—C6 | 120.3 | C19—C20—H20 | 120.1 |
C1—C6—C5 | 120.9 (9) | C19—C20—C21 | 119.9 (7) |
C1—C6—H6 | 119.6 | H20—C20—C21 | 120.1 |
C5—C6—H6 | 119.6 | C20—C21—H21 | 120.2 |
P—C7—C8 | 119.3 (6) | C20—C21—C22 | 119.6 (7) |
P—C7—C12 | 120.4 (6) | H21—C21—C22 | 120.2 |
C8—C7—C12 | 120.3 (7) | C21—C22—H22 | 119.8 |
C7—C8—H8 | 120.9 | C21—C22—C23 | 120.4 (7) |
C7—C8—C9 | 118.1 (7) | H22—C22—C23 | 119.8 |
H8—C8—C9 | 120.9 | C22—C23—H23 | 119.8 |
C8—C9—H9 | 119.3 | C22—C23—C24 | 120.4 (7) |
C8—C9—C10 | 121.4 (8) | H23—C23—C24 | 119.8 |
H9—C9—C10 | 119.3 | C19—C24—C23 | 119.7 (7) |
C9—C10—H10 | 120.1 | C19—C24—H24 | 120.2 |
C9—C10—C11 | 119.9 (7) | C23—C24—H24 | 120.2 |
H10—C10—C11 | 120.1 | ||
Pdi—I1—Pd—I1i | 0.0 | C8—C7—C12—C11 | −0.5 (12) |
Pdi—I1—Pd—I2 | 23.0 (6) | C1—P—C13—C14 | −106.1 (7) |
Pdi—I1—Pd—I3 | −179.59 (3) | C1—P—C13—C18 | 72.9 (7) |
C7—P—C1—C2 | −81.2 (7) | C7—P—C13—C14 | 132.1 (7) |
C7—P—C1—C6 | 99.7 (7) | C7—P—C13—C18 | −48.9 (7) |
C13—P—C1—C2 | 158.9 (6) | C19—P—C13—C14 | 11.9 (8) |
C13—P—C1—C6 | −20.3 (8) | C19—P—C13—C18 | −169.1 (6) |
C19—P—C1—C2 | 39.0 (7) | P—C13—C14—C15 | −179.4 (6) |
C19—P—C1—C6 | −140.2 (7) | C18—C13—C14—C15 | 1.6 (12) |
P—C1—C2—C3 | −178.7 (6) | C13—C14—C15—C16 | −1.6 (12) |
C6—C1—C2—C3 | 0.5 (12) | C14—C15—C16—C17 | 0.8 (12) |
C1—C2—C3—C4 | 0.8 (12) | C15—C16—C17—C18 | 0.2 (12) |
C2—C3—C4—C5 | −1.3 (13) | C16—C17—C18—C13 | −0.2 (12) |
C3—C4—C5—C6 | 0.4 (14) | P—C13—C18—C17 | −179.7 (6) |
C4—C5—C6—C1 | 1.0 (14) | C14—C13—C18—C17 | −0.7 (12) |
P—C1—C6—C5 | 177.7 (7) | C1—P—C19—C20 | −129.3 (6) |
C2—C1—C6—C5 | −1.4 (13) | C1—P—C19—C24 | 52.6 (7) |
C1—P—C7—C8 | −150.3 (6) | C7—P—C19—C20 | −8.7 (7) |
C1—P—C7—C12 | 30.7 (7) | C7—P—C19—C24 | 173.3 (6) |
C13—P—C7—C8 | −28.6 (7) | C13—P—C19—C20 | 110.2 (6) |
C13—P—C7—C12 | 152.4 (6) | C13—P—C19—C24 | −67.8 (7) |
C19—P—C7—C8 | 91.6 (7) | P—C19—C20—C21 | −177.4 (6) |
C19—P—C7—C12 | −87.4 (7) | C24—C19—C20—C21 | 0.6 (11) |
P—C7—C8—C9 | −179.7 (6) | C19—C20—C21—C22 | 0.6 (11) |
C12—C7—C8—C9 | −0.7 (12) | C20—C21—C22—C23 | −1.1 (11) |
C7—C8—C9—C10 | 1.5 (12) | C21—C22—C23—C24 | 0.3 (11) |
C8—C9—C10—C11 | −1.0 (13) | C22—C23—C24—C19 | 1.0 (11) |
C9—C10—C11—C12 | −0.2 (13) | P—C19—C24—C23 | 176.7 (6) |
C10—C11—C12—C7 | 0.9 (13) | C20—C19—C24—C23 | −1.4 (11) |
P—C7—C12—C11 | 178.5 (7) |
Symmetry code: (i) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | (C24H20P)2[Pd2I6] |
Mr | 1652.94 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 150 |
a, b, c (Å) | 12.8951 (11), 14.4427 (13), 13.9409 (12) |
β (°) | 106.613 (1) |
V (Å3) | 2488.0 (4) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 4.54 |
Crystal size (mm) | 0.39 × 0.24 × 0.05 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD diffractometer |
Absorption correction | Gaussian (SADABS; Sheldrick, 2007) |
Tmin, Tmax | 0.268, 0.805 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15011, 4154, 2914 |
Rint | 0.040 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.101, 1.14 |
No. of reflections | 4154 |
No. of parameters | 262 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0253P)2 + 19.5288P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 1.19, −0.98 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), ORTEP-3 for Windows (Farrugia, 1997), SHELXTL (Sheldrick, 2001) and local programs.
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.