Acta Cryst. (2009). E65, m1588 [ doi:10.1107/S1600536809047771 ]
![[kappa]](/logos/entities/kappa_rmgif.gif)
2N,N')diiodidopalladium(II)The asymmetric unit of the title complex, [PdI2(C10H8N2)], contains one half of the formula unit. The Pd2+ ion is located on a twofold rotation axis and is four-coordinated in a slightly distorted square-planar environment by two N atoms of the chelating 2,2'-bipyridine ligand and two iodide ions. The compound displays intermolecular ![[pi]](/logos/entities/pi_rmgif.gif)
- interactions between the pyridine rings of the ligand, the shortest centroid-centroid distance being 4.220 (4) Å.
To a solution of Na2PdCl4 (0.1991 g, 0.677 mmol) in H2O (20 ml) were added KI (1.1230 g, 6.765 mmol) and 2,2'-bipyridine (0.1057 g, 0.677 mmol), and refluxed for 3 h. The precipitate obtained was separated by filtration, and washed with water and acetone, and dried at 70 °C, to give a red-brown powder (0.2999 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH3CN solution.
H atoms were positioned geometrically and allowed to ride on their respective parent atoms [C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C)].
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).
![[Figure 1]](./is2486fig1thm.gif)
| Fig. 1. The structure of the title complex, with displacement ellipsoids drawn at the 50% probability level for non-H atoms [Symmetry code: (a) -x, y, 1/2 - z]. |
![[Figure 2]](./is2486fig2thm.gif)
| Fig. 2. Crystal packing of the title complex. |
| [PdI2(C10H8N2)] | F(000) = 936 |
| Mr = 516.38 | Dx = 2.831 Mg m−3 |
| Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -C 2yc | Cell parameters from 550 reflections |
| a = 17.232 (4) Å | θ = 2.4–24.4° |
| b = 9.8273 (19) Å | µ = 6.60 mm−1 |
| c = 7.6868 (15) Å | T = 293 K |
| β = 111.438 (3)° | Needle, brown |
| V = 1211.6 (4) Å3 | 0.25 × 0.05 × 0.05 mm |
| Z = 4 |
| Bruker SMART 1000 CCD diffractometer | 1240 independent reflections |
| Radiation source: fine-focus sealed tube | 1049 reflections with I > 2σ(I) |
| graphite | Rint = 0.025 |
| φ and ω scans | θmax = 26.4°, θmin = 2.4° |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | h = −21→13 |
| Tmin = 0.139, Tmax = 0.719 | k = −11→12 |
| 3458 measured reflections | l = −9→9 |
| 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) = 0.071 | H-atom parameters constrained |
| S = 1.06 | w = 1/[σ2(Fo2) + (0.0328P)2] where P = (Fo2 + 2Fc2)/3 |
| 1240 reflections | (Δ/σ)max < 0.001 |
| 69 parameters | Δρmax = 0.60 e Å−3 |
| 0 restraints | Δρmin = −0.65 e Å−3 |
| [PdI2(C10H8N2)] | V = 1211.6 (4) Å3 |
| Mr = 516.38 | Z = 4 |
| Monoclinic, C2/c | Mo Kα radiation |
| a = 17.232 (4) Å | µ = 6.60 mm−1 |
| b = 9.8273 (19) Å | T = 293 K |
| c = 7.6868 (15) Å | 0.25 × 0.05 × 0.05 mm |
| β = 111.438 (3)° |
| Bruker SMART 1000 CCD diffractometer | 1240 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 1049 reflections with I > 2σ(I) |
| Tmin = 0.139, Tmax = 0.719 | Rint = 0.025 |
| 3458 measured reflections | θmax = 26.4° |
| R[F2 > 2σ(F2)] = 0.032 | H-atom parameters constrained |
| wR(F2) = 0.071 | Δρmax = 0.60 e Å−3 |
| S = 1.06 | Δρmin = −0.65 e Å−3 |
| 1240 reflections | Absolute structure: ? |
| 69 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
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 | ||
| Pd1 | 0.0000 | −0.19021 (5) | 0.2500 | 0.03813 (17) | |
| I1 | 0.10045 (3) | −0.37899 (4) | 0.43052 (5) | 0.06273 (19) | |
| N1 | 0.0755 (3) | −0.0277 (4) | 0.3822 (6) | 0.0431 (10) | |
| C1 | 0.1524 (4) | −0.0339 (6) | 0.5132 (7) | 0.0546 (14) | |
| H1 | 0.1767 | −0.1188 | 0.5499 | 0.066* | |
| C2 | 0.1966 (4) | 0.0802 (7) | 0.5952 (9) | 0.0655 (17) | |
| H2 | 0.2495 | 0.0725 | 0.6871 | 0.079* | |
| C3 | 0.1617 (4) | 0.2050 (6) | 0.5399 (9) | 0.0656 (18) | |
| H3 | 0.1902 | 0.2837 | 0.5944 | 0.079* | |
| C4 | 0.0840 (4) | 0.2128 (6) | 0.4029 (9) | 0.0611 (17) | |
| H4 | 0.0597 | 0.2972 | 0.3627 | 0.073* | |
| C5 | 0.0418 (4) | 0.0954 (5) | 0.3248 (8) | 0.0446 (12) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Pd1 | 0.0378 (3) | 0.0339 (3) | 0.0385 (3) | 0.000 | 0.0091 (2) | 0.000 |
| I1 | 0.0636 (3) | 0.0471 (3) | 0.0633 (3) | 0.01213 (18) | 0.0064 (2) | 0.00869 (16) |
| N1 | 0.043 (2) | 0.043 (2) | 0.045 (2) | −0.002 (2) | 0.018 (2) | −0.0005 (19) |
| C1 | 0.046 (3) | 0.062 (4) | 0.050 (3) | −0.003 (3) | 0.012 (3) | −0.004 (3) |
| C2 | 0.050 (4) | 0.087 (5) | 0.056 (4) | −0.019 (4) | 0.016 (3) | −0.015 (3) |
| C3 | 0.065 (4) | 0.060 (4) | 0.082 (4) | −0.029 (4) | 0.039 (4) | −0.028 (3) |
| C4 | 0.067 (4) | 0.050 (3) | 0.074 (4) | −0.018 (3) | 0.036 (4) | −0.015 (3) |
| C5 | 0.050 (3) | 0.039 (3) | 0.056 (3) | −0.001 (2) | 0.033 (3) | −0.002 (2) |
| Pd1—N1 | 2.076 (4) | C2—C3 | 1.364 (9) |
| Pd1—N1i | 2.076 (4) | C2—H2 | 0.9300 |
| Pd1—I1i | 2.5704 (6) | C3—C4 | 1.370 (9) |
| Pd1—I1 | 2.5704 (6) | C3—H3 | 0.9300 |
| N1—C1 | 1.341 (7) | C4—C5 | 1.378 (7) |
| N1—C5 | 1.345 (6) | C4—H4 | 0.9300 |
| C1—C2 | 1.372 (8) | C5—C5i | 1.480 (12) |
| C1—H1 | 0.9300 | ||
| N1—Pd1—N1i | 79.4 (2) | C3—C2—C1 | 119.0 (6) |
| N1—Pd1—I1i | 175.85 (12) | C3—C2—H2 | 120.5 |
| N1i—Pd1—I1i | 96.48 (12) | C1—C2—H2 | 120.5 |
| N1—Pd1—I1 | 96.48 (12) | C2—C3—C4 | 119.0 (6) |
| N1i—Pd1—I1 | 175.85 (12) | C2—C3—H3 | 120.5 |
| I1i—Pd1—I1 | 87.61 (3) | C4—C3—H3 | 120.5 |
| C1—N1—C5 | 118.5 (5) | C3—C4—C5 | 120.0 (6) |
| C1—N1—Pd1 | 127.1 (4) | C3—C4—H4 | 120.0 |
| C5—N1—Pd1 | 114.4 (4) | C5—C4—H4 | 120.0 |
| N1—C1—C2 | 122.6 (6) | N1—C5—C4 | 120.9 (6) |
| N1—C1—H1 | 118.7 | N1—C5—C5i | 115.9 (3) |
| C2—C1—H1 | 118.7 | C4—C5—C5i | 123.2 (4) |
| N1i—Pd1—N1—C1 | −178.7 (6) | C2—C3—C4—C5 | 0.8 (9) |
| I1—Pd1—N1—C1 | 2.1 (5) | C1—N1—C5—C4 | −2.1 (8) |
| N1i—Pd1—N1—C5 | 0.5 (3) | Pd1—N1—C5—C4 | 178.6 (4) |
| I1—Pd1—N1—C5 | −178.7 (3) | C1—N1—C5—C5i | 177.9 (6) |
| C5—N1—C1—C2 | 2.3 (9) | Pd1—N1—C5—C5i | −1.4 (7) |
| Pd1—N1—C1—C2 | −178.5 (4) | C3—C4—C5—N1 | 0.6 (9) |
| N1—C1—C2—C3 | −0.9 (10) | C3—C4—C5—C5i | −179.4 (6) |
| C1—C2—C3—C4 | −0.6 (10) |
| Symmetry codes: (i) −x, y, −z+1/2. |
| Pd1—N1 | 2.076 (4) | Pd1—I1 | 2.5704 (6) |
| N1—Pd1—N1i | 79.4 (2) |
| Symmetry codes: (i) −x, y, −z+1/2. |
This work was supported by a Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).
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The title complex, [PdI2(bipy)] (where bipy is 2,2'-bipyridine, C10H8N2), is isomorphous with [PdBr2(bipy)] (Smeets et al., 1997), whereas [PdCl2(bipy)] crystallized in the orthorhombic space group C2221 (Maekawa et al., 1991).
The asymmetric unit of the title complex contains one half of the formula unit. The complex is disposed about a twofold rotation axis through Pd atom with the special position at (0, y, 1/4) (Wyckoff letter e). The Pd2+ ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the chelating 2,2'-bipyridine ligand and two iodide ions (Fig. 1). The main contribution to the distortion is the tight N1—Pd1—N1a [symmetry code: (a) -x, y, 1/2 - z] chelate angle [79.4 (2)°], which results in non-linear trans arrangement [<N1—Pd1—I1a = 175.85 (12)°]. The complex displays intermolecular π-π interactions between adjacent pyridine rings of the lignad (the symmetry operation for second plane x, -y, -1/2 + z), with a shortest centroid-centroid distance of 4.220 (4) Å (Fig. 2).