Abstract
C22H16Cl2N2Pd2, monoclinic, P21/c (no. 14), a = 7.2249(6) Å, b = 17.0538(14) Å, c = 8.4291(7) Å, β = 112.211(2)°, V = 961.50(14) Å3, Z = 2, Rgt(F) = 0.0217, wRref(F2) = 0.0496, T = 200(2) K.
The crystal structure is shown in the figure. Tables 1–3 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Data collection and handling.
| Crystal: | Yellow, block, size 0.09×0.20×0.36 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 21.59 cm−1 |
| Diffractometer, scan mode: | Bruker SMART 1000 CCD, φ and ω scans |
| 2θmax: | 52.07° |
| N(hkl)measured, N(hkl)unique: | 5610, 1847 |
| N(param)refined: | 127 |
| Programs: | SHELX [6], WinGX [7], PLATON [8] |
Atomic coordinates and isotropic displacement parameters (Å2).
| Atom | Site | x | y | z | Uiso |
|---|---|---|---|---|---|
| H(1) | 4e | 0.2297 | 0.3293 | 0.2095 | 0.042 |
| H(2) | 4e | 0.0660 | 0.2521 | −0.0314 | 0.049 |
| H(3) | 4e | −0.0317 | 0.3064 | −0.3046 | 0.055 |
| H(4) | 4e | 0.0400 | 0.4378 | −0.3365 | 0.048 |
| H(7) | 4e | 0.1418 | 0.5646 | −0.3391 | 0.045 |
| H(8) | 4e | 0.2587 | 0.6930 | −0.3158 | 0.048 |
| H(9) | 4e | 0.4285 | 0.7474 | −0.0436 | 0.045 |
| H(10) | 4e | 0.4847 | 0.6718 | 0.2008 | 0.041 |
Atomic coordinates and displacement parameters (Å2).
| Atom | Site | x | y | z | U11 | U22 | U33 | U12 | U13 | U23 |
|---|---|---|---|---|---|---|---|---|---|---|
| Pd(1) | 4e | 0.38634(3) | 0.50092(2) | 0.27423(2) | 0.0333(1) | 0.0223(1) | 0.0210(1) | 0.00044(9) | 0.00955(9) | −0.00016(8) |
| Cl(1) | 4e | 0.4173(1) | 0.41079(5) | 0.50327(9) | 0.0725(6) | 0.0331(4) | 0.0264(4) | −0.0101(4) | 0.0113(4) | 0.0002(3) |
| N(1)a | 4e | 0.2342(4) | 0.4287(2) | 0.0812(3) | 0.026(1) | 0.030(2) | 0.029(1) | 0.002(1) | 0.011(1) | −0.004(1) |
| C(11A)a | 4e | 0.2342(4) | 0.4287(2) | 0.0812(3) | 0.026(1) | 0.030(2) | 0.029(1) | 0.002(1) | 0.011(1) | −0.004(1) |
| C(1) | 4e | 0.1917(4) | 0.3515(2) | 0.0984(4) | 0.036(2) | 0.033(2) | 0.039(2) | −0.003(1) | 0.017(1) | −0.005(1) |
| C(2) | 4e | 0.0938(5) | 0.3056(2) | −0.0448(4) | 0.043(2) | 0.037(2) | 0.048(2) | −0.012(1) | 0.023(2) | −0.013(2) |
| C(3) | 4e | 0.0369(5) | 0.3376(2) | −0.2065(4) | 0.043(2) | 0.055(2) | 0.040(2) | −0.019(2) | 0.018(2) | −0.019(2) |
| C(4) | 4e | 0.0799(4) | 0.4154(2) | −0.2253(4) | 0.037(2) | 0.055(2) | 0.027(2) | −0.006(2) | 0.012(1) | −0.006(2) |
| C(5) | 4e | 0.1818(4) | 0.4606(2) | −0.0813(3) | 0.023(1) | 0.036(2) | 0.028(2) | 0.002(1) | 0.010(1) | −0.004(1) |
| C(6) | 4e | 0.2428(4) | 0.5422(2) | −0.0827(3) | 0.027(1) | 0.033(2) | 0.026(2) | 0.007(1) | 0.012(1) | 0.003(1) |
| C(7) | 4e | 0.2114(4) | 0.5868(2) | −0.2292(4) | 0.034(2) | 0.049(2) | 0.028(2) | 0.006(2) | 0.010(1) | 0.007(1) |
| C(8) | 4e | 0.2804(4) | 0.6628(2) | −0.2157(4) | 0.039(2) | 0.046(2) | 0.037(2) | 0.012(2) | 0.017(1) | 0.019(2) |
| C(9) | 4e | 0.3818(5) | 0.6948(2) | −0.0544(4) | 0.042(2) | 0.030(2) | 0.048(2) | 0.010(1) | 0.025(2) | 0.013(1) |
| C(10) | 4e | 0.4147(4) | 0.6498(2) | 0.0907(4) | 0.038(2) | 0.029(2) | 0.038(2) | 0.005(1) | 0.019(1) | 0.001(1) |
| C(11)a | 4e | 0.3473(4) | 0.5738(2) | 0.0774(3) | 0.031(1) | 0.028(1) | 0.029(1) | 0.006(1) | 0.013(1) | 0.002(1) |
| N(1A)a | 4e | 0.3473(4) | 0.5738(2) | 0.0774(3) | 0.031(1) | 0.028(1) | 0.029(1) | 0.006(1) | 0.013(1) | 0.002(1) |
aDisordered, occupancy factor: 0.5.
Source of material
To a solution of 2-phenylpyridine (ppyH; 0.3658 g, 2.357 mmol) and 2,6-pyridinedicarboxylic acid (0.1745 g, 1.044 mmol) in EtOH (30 mL)/H2O (20 mL) was added Na2PdCl4 (0.3047 g, 1.036 mmol) and refluxed for 3 h. The formed precipitate was separated by filtration, washed with H2O and acetone, and dried at 50 °C, to give a yellow powder (0.2545 g). Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation from an N,N-dimethylformamide solution at 60 °C.
Experimental details
Hydrogen atoms were positioned geometrically and allowed to ride on their parent atoms with d(C—H) = 0.95 Å and Uiso(H) = 1.2Ueq(C). The structure shows a 1:1 disorder in the sites N1 and C11, (not shown in the figure).
Discussion
This contribution is part of my continuing interest in the structural chemistry of palladium 2-phenylpyridine (ppyH) complexes [1, 2]. The title complex [Pd2(μ-Cl)2(ppy)2] was unexpectedly obtained from the reaction of Na2PdCl4, 2,6-pyridinedicarboxylic acid and ppyH, and has a trans chlorido-bridged dimeric structure, whereas the cis analogue was prepared by the reaction of 2-phenylpyridine with Na2PdCl4 or Li2PdCl4, and its crystal structure was reported previously [3–5]. Both cis- and trans-complexes crystallize in the monoclinic space group P21/c, but the latter has an inversion center in the middle of the molecule, and therefore the asymmetric unit contains one half of the complex. In the title crystal structure, each Pd(II) ion has a slightly distorted square-planar coordination defined by one N atom and one C atom from the ortho-metalated anionic 2-(2-pyridyl)phenyl ligand and two bridging chlorido ligands. The main contribution to the distortion is the tight N1—Pd1—C11 chelate angle of 81.27(12)°. The complex is nearly planar: the Pd2Cl2 moiety is exactly plane, and the dihedral angle between the moiety and the nearly planar chelating ligand (maximum deviation = 0.053(3) Å) is 4.30(5)°. The pyridine and phenyl rings are almost parallel: the dihedral angle between the ring planes is 3.4(1)°. In the complex, the Pd⋯Pd distance is 3.5298(4) Å, and Pd—C and Pd—N bond lengths are almost equal (2.001(3) Å and 2.006(3) Å). In the crystal, the molecules are stacked in columns along [100]. In the columns, several intermolecular π−π stacking interactions between adjacent six-membered rings are present. For Cg1 (the centroid of ring N1—C5) and Cg2i (the centroid of ring C6—C11; symmetry code i: 1−x, 1−y, −z), the centroid-centroid distance is 3.704(2) Å.
Acknowledgements:
This work was supported by Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2009–0094055). The author thanks the KBSI, Jeonju Center, for the X-ray data collection.
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©2016 Kwang Ha, published by De Gruyter.
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