Bis(azido-κN)(di-2-pyridylamine-κ2 N 2,N 2′)palladium(II)

In the title complex, [Pd(N3)2(C10H9N3)], the PdII ion is in a slightly distorted square-planar coordination environment. The ligator atoms comprise the two pyridine N atoms of the chelating di-2-pyridylamine (dpa) ligand and two N atoms from two azide anions. The dpa ligand coordinates the Pd atom in a boat conformation, the dihedral angle between the pyridine rings being 24.4 (1)°. The pyridine rings are somewhat inclined to the least-squares plane of the PdN4 unit, making dihedral angles of 29.02 (9) and 26.47 (9)°. The azide ligands are slightly bent, with N—N—N angles of 173.0 (4) and 174.2 (4)°. In the crystal, molecules are connected by N—H⋯N and C—H⋯N hydrogen bonds, forming chains along the c axis. When viewed down the b axis, successive chains are stacked in opposite directions. Intramolecular C—H⋯N hydrogen bonds are also observed.

In the title complex, [Pd(N 3 ) 2 (C 10 H 9 N 3 )], the Pd II ion is in a slightly distorted square-planar coordination environment. The ligator atoms comprise the two pyridine N atoms of the chelating di-2-pyridylamine (dpa) ligand and two N atoms from two azide anions. The dpa ligand coordinates the Pd atom in a boat conformation, the dihedral angle between the pyridine rings being 24.4 (1) . The pyridine rings are somewhat inclined to the least-squares plane of the PdN 4 unit, making dihedral angles of 29.02 (9) and 26.47 (9) . The azide ligands are slightly bent, with N-N-N angles of 173.0 (4) and 174.2 (4) . In the crystal, molecules are connected by N-HÁ Á ÁN and C-HÁ Á ÁN hydrogen bonds, forming chains along the c axis. When viewed down the b axis, successive chains are stacked in opposite directions. Intramolecular C-HÁ Á ÁN hydrogen bonds are also observed.
In the title complex, [Pd(N 3 ) 2 (dpa)], the Pd II ion is four-coordinated in a slightly distorted square-planar environment by the two pyridine N atoms of the chelating dpa ligand and two N atoms from two azide anions (  Table 2). When viewed down the b axis, successive chains are stacked in opposite directions. Intramolecular C-H···N hydrogen bonds are also observed ( Table   2).

Experimental
To a solution of Na 2 PdCl 4 (0.1451 g, 0.493 mmol) in MeOH (30 ml) were added NaN 3 (0.3050 g, 4.692 mmol) and di-2pyridylamine (0.0860 g, 0.502 mmol), and stirred for 5 h at room temperature. The formed precipitate was separated by filtration and washed with H 2 O and acetone, and dried at 50 °C, to give a yellow powder (0.1604 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH 3 CN/acetone solution.

Refinement
Carbon-bound H atoms were positioned geometrically and allowed to ride on their respective parent atoms: C-H = 0.95 Å with U iso (H) = 1.2U eq (C). Nitrogen-bound H atom was located from the difference Fourier map then allowed to ride on its parent atom in the final cycles of refinement with N-H = 0.92 Å and U iso (H) = 1.5 U eq (N). The highest peak (0.71 e Å -3 ) and the deepest hole (-0.41 e Å -3 ) in the difference Fourier map are located 1.07 Å and 1.54 Å, respectively, from the Pd1 atom.

Computing details
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).  A structure detail of the title complex, with displacement ellipsoids drawn at the 50% probability level for non-H atoms. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 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 (Å 2 )
x y z U iso */U eq  (5)