Bis(acetato-κO)(di-2-pyridyl­amine-κ2 N 2,N 2′)palladium(II)

Kwang Ha

doi:10.1107/S1600536812012093

. 2012 Mar 31;68(Pt 4):m502. doi: 10.1107/S1600536812012093

Bis(acetato-κO)(di-2-pyridylamine-κ² N ²,N ^2′)palladium(II)

Kwang Ha ^a,^*

PMCID: PMC3343887 PMID: 22589855

Abstract

In the title complex, [Pd(CH₃COO)₂(C₁₀H₉N₃)], the Pd^II ion is four-coordinated in a slightly distorted square-planar environment by two pyridine N atoms of the chelating di-2-pyridylamine (dpa) ligand and two O atoms from two anionic acetate ligands. The dpa ligand coordinates the Pd^II atom in a boat conformation of the resulting chelate ring; the dihedral angle between the pyridine rings is 39.3 (2)°. The two acetate anions coordinate the Pd^II atom as monodentate ligands and are located on the same sides of the PdN₂O₂ unit plane. The carboxylate groups of the anionic ligands appear to be delocalized on the basis of the C—O bond lengths. Two complex molecules are assembled through intermolecular N—H⋯O hydrogen bonds, forming a dimer-type species. Intermolecular C—H⋯O hydrogen bonds further stabilize the crystal structure.

Related literature

For the crystal structures of the related Pd^II complexes [PdX ₂(dpa)] (X = Cl or Br), see: Rauterkus et al. (2003 ▶); Yao et al. (2003 ▶).

Experimental

Crystal data

[Pd(C₂H₃O₂)₂(C₁₀H₉N₃)]
M _r = 395.69
Monoclinic,
a = 8.565 (3) Å
b = 12.245 (5) Å
c = 14.230 (5) Å
β = 95.406 (8)°
V = 1485.8 (10) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 200 K
0.24 × 0.10 × 0.10 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.777, T _max = 1.000
8823 measured reflections
2925 independent reflections
1807 reflections with I > 2σ(I)
R _int = 0.102

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.116
S = 0.92
2925 reflections
205 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.99 e Å⁻³
Δρ_min = −0.81 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; 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.

Supplementary Material

Crystal structure: contains datablock(s) global. DOI: 10.1107/S1600536812012093/zq2158sup1.cif

e-68-0m502-sup1.cif^{(24.2KB, cif)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

Pd1—N3	2.003 (5)
Pd1—O1	2.004 (4)
Pd1—N1	2.004 (4)
Pd1—O3	2.006 (4)

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N3—Pd1—N1

89.13 (19)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O2ⁱ	0.93 (6)	1.83 (7)	2.762 (7)	179 (6)
C2—H2⋯O4ⁱⁱ	0.95	2.58	3.302 (9)	133

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by the Priority Research Centers Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (2011–0030747).

supplementary crystallographic information

Comment

Crystal structures of Pd^II complexes with di-2-pyridylamine (dpa; C₁₀H₉N₃) and halogen ions, [PdX₂(dpa)] (X = Cl or Br), have been reported previously (Rauterkus et al., 2003; Yao et al., 2003).

In the title complex, [Pd(C₂H₃O₂)₂(dpa)], the Pd^II ion is four-coordinated in a slightly distorted square-planar environment by two pyridine N atoms of the chelating dpa ligand and two O atoms from two anionic acetato ligands (Fig. 1). The dpa ligand coordinates the Pd atom in a boat conformation. The dihedral angle between the least-squares planes of the two pyridine rings is 39.3 (2)°. The Pd—N and Pd—O bond lengths are nearly equivalent [Pd—N: 2.003 (5) and 2.004 (5) Å; Pd—O: 2.004 (4) and 2.006 (4) Å] (Table 1). The two acetate anions coordinate the Pd atom as monodentate ligands via one O atom and are located on the same sides of the PdN₂O₂ unit plane. The carboxylate groups of the anionic ligands appear to be delocalized on the basis of the C—O bond lengths [C—O: 1.217 (7)–1.274 (8) Å]. Two complex molecules are assembled through intermolecular N—H···O hydrogen bonds, forming a dimer-type species (Fig. 2 and Table 2). Intra- and intermolecular C—H···O hydrogen bonds stabilize further the crystal structure (Table 2). The complex molecules are stacked into columns along the a axis. In the columns, several intermolecular π···π interactions between the pyridine rings are present, the shortest ring centroid···centroid distance being 4.646 (4) Å.

Experimental

To a solution of Pd(CH₃CO₂)₂ (0.1128 g, 0.502 mmol) in acetone (30 ml) was added di-2-pyridylamine (0.0873 g, 0.510 mmol) and stirred for 20 h at room temperature. After removal of the formed black precipitate by filtration, the solvent of the filtrate was evaporated, and the residue was washed with ether and dried under vacuum, to give a yellow powder (0.1462 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₃CN solution.