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

Kwang Ha

doi:10.1107/S1600536812013074

. 2012 Mar 31;68(Pt 4):m519. doi: 10.1107/S1600536812013074

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

Kwang Ha ^a,^*

PMCID: PMC3343901 PMID: 22589869

Abstract

In the title complex, [Pd(N₃)₂(C₁₀H₉N₃)], 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 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.

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(N₃)₂(C₁₀H₉N₃)]
M _r = 361.66
Monoclinic,
a = 17.5552 (15) Å
b = 6.9773 (6) Å
c = 19.6654 (17) Å
β = 99.206 (2)°
V = 2377.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 1.57 mm⁻¹
T = 200 K
0.20 × 0.14 × 0.09 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.901, T _max = 1.000
7041 measured reflections
2322 independent reflections
1751 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.073
S = 1.06
2322 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.71 e Å⁻³
Δρ_min = −0.41 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/S1600536812013074/fj2539sup1.cif

e-68-0m519-sup1.cif^{(22.2KB, cif)}

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

Table 1. Selected bond lengths (Å).

Pd1—N4	2.001 (3)
Pd1—N7	2.018 (3)
Pd1—N1	2.040 (3)
Pd1—N3	2.046 (3)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯N9ⁱ	0.92	2.31	3.208 (4)	165
C1—H1⋯N4	0.95	2.35	2.816 (5)	110
C4—H4⋯N6ⁱ	0.95	2.40	3.175 (5)	138
C10—H10⋯N7	0.95	2.35	2.861 (5)	113

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Symmetry code: (i) Inline graphic .

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(N₃)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 (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 24.4 (1)°. The pyridine rings are somewhat inclined to the least-squares plane of the PdN₄ unit [maximum deviation = 0.016 (2) Å], making dihedral angles of 29.02 (9)° and 26.47 (9)°. The Pd—N(azide) and Pd—N(dpa) bond lengths are nearly equivalent [Pd—N: 2.001 (3)–2.046 (3) Å] (Table 1). The azide ligands are slightly bent with the bond angles of <N4—N5—N6 = 173.0 (4)° and <N7—N8—N9 = 174.2 (4)°. But, the N—N bond lengths of the ligands are almost equal [N—N: 1.146 (4)–1.212 (4) Å]. In the crystal, the complex molecules are connected by intermolecular N—H···N and C—H···N hydrogen bonds, forming chains along the c axis (Fig. 2 and 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 Na₂PdCl₄ (0.1451 g, 0.493 mmol) in MeOH (30 ml) were added NaN₃ (0.3050 g, 4.692 mmol) and di-2-pyridylamine (0.0860 g, 0.502 mmol), and stirred for 5 h at room temperature. The formed precipitate was separated by filtration and washed with H₂O 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 CH₃CN/acetone solution.