Dichlorido[1-(1-naphthyl­meth­yl)-3-(2-pyrid­yl)-1H-pyrazole-κ2 N 2,N 3]palladium(II)

Chun-Sen Liu; Guang-Hui Sun; Liang-Qi Guo

doi:10.1107/S1600536807062927

. 2007 Dec 6;64(Pt 1):m69. doi: 10.1107/S1600536807062927

Dichlorido[1-(1-naphthylmethyl)-3-(2-pyridyl)-1H-pyrazole-κ² N ²,N ³]palladium(II)

Chun-Sen Liu ^a,^b,^*, Guang-Hui Sun ^a, Liang-Qi Guo ^a

PMCID: PMC2914949 PMID: 21200638

Abstract

In the title compound, [PdCl₂(C₁₉H₁₅N₃)], the Pd^II centre is four-coordinated by two N-atom donors from one 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]naphthalene (L) ligand and by two Cl atoms in a distorted square-planar coordination geometry. In the crystal structure, adjacent Pd^II mononuclear units form intermolecular C—H⋯π interactions involving the benzene and pyridine rings of different L ligands and π–π stacking interactions between the pyrazolyl-pyridine and naphthalene rings of neighbouring L ligands, with a centroid–centroid separation of 3.522 (1) Å.

Related literature

For related literature, see: Bell et al. (2003 ▶); Janiak (2000 ▶); Liu, Li et al. (2007 ▶); Liu, Zhang et al. (2007 ▶); Paul et al. (2004 ▶); Singh et al. (2003 ▶); Sony & Ponnuswamy (2006 ▶); Steel (2005 ▶); Ward et al. (2001 ▶); Zhang et al. (2005 ▶); Zou et al. (2004 ▶).

Experimental

Crystal data

[PdCl₂(C₁₉H₁₅N₃)]
M _r = 462.64
Orthorhombic,
a = 9.330 (6) Å
b = 12.139 (8) Å
c = 15.918 (11) Å
V = 1803 (2) Å³
Z = 4
Mo Kα radiation
μ = 1.33 mm⁻¹
T = 293 (2) K
0.20 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.772, T _max = 0.848
10453 measured reflections
3702 independent reflections
3340 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.054
S = 1.03
3702 reflections
226 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Absolute structure: Flack (1983 ▶), 1580 Friedel pairs
Flack parameter: 0.00 (3)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 ▶); molecular graphics: SHELXTL (Bruker, 1998 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536807062927/bi2262sup1.cif

e-64-00m69-sup1.cif^{(20KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807062927/bi2262Isup2.hkl

e-64-00m69-Isup2.hkl^{(181.5KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17A⋯Cg1ⁱ	0.93	2.89	3.602	134
C18—H18A⋯Cg2ⁱⁱ	0.93	3.05	3.803	139

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of atoms C1–C5/C10 and Cg2 is the centroid of atoms Pd1/N2/C14/C15/N3.

Acknowledgments

This work was supported by the Startup Fund for PhDs in Natural Scientific Research of Zhengzhou University of Light Industry (No. 2008 to C-SL). The authors also thank Nankai University and Henan Provincial Key Laboratory of Surface & Interface Science for supporting this research.

supplementary crystallographic information

Comment

In recent years, attention has been focused on the synthetic approach and the structural control of metal-organic coordination architectures with ligands based on pyrazolyl-pyridine chelating units (Steel, 2005; Ward et al., 2001). In this field, Ward and co-workers have reported novel functional complexes through the use of 3-(2-pyridyl)pyrazole and/or 3-(2-pyridyl)pyrazole-based ligands (Bell et al., 2003; Paul et al., 2004; Singh et al., 2003; Ward et al., 2001; Zou et al., 2004). Recently, we have reported the preparation of a non-planar ligand, 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]naphthalene (denoted L) (Liu & Li et al., 2007; Liu & Zhang et al., 2007; Zhang et al., 2005). We report here the crystal structure of a palladium complex of this ligand, [(L)PdCl₂].

In the title compound, the Pd^II centre is four-coordinated by two N-atom donors from one L ligand and two Cl atoms. The coordination geometry around the Pd^II center can be described as a slightly distorted square-plane (Fig. 1). In the crystal structure, the Pd^II mononuclear units form intermolecular π···π stacking interactions between pyrazolyl-pyridine and naphthalene rings of neighbouring L ligands with a centroid–centroid separation of 3.522 (1) Å (Janiak, 2000) and C—H···π interactions involving C1/C2/C3/C4/C5/C10 (centroid Cg1) benzene rings of the L ligands as well as five-membered chelate rings Pd1/N2/C14/C15/N3 (centroid Cg2) (Sony and Ponnuswamy, 2006) (Fig. 2).

Experimental

The ligand 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]naphthalene (L) was synthesized according to the method reported in the literature (Liu & Li et al., 2007; Liu & Zhang et al., 2007; Zhang et al., 2005). A solution of PdCl₂ (0.1 mmol) in methanol (15 ml) and acetonitrile (5 ml) was added to L (0.1 mmol). A yellow solid formed was filtered off and the resulting solution was kept at room temperature. Yellow single crystals suitable for X-ray analysis were obtained by slow evaporation of the solvent after several days. Yield: ca 30%. Elemental analysis calculated: C 49.32, H 3.27, N 9.08%; found: C 49.47, H 3.16, N 9.20%.