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Acta Cryst. (2008). E64, m69    [ doi:10.1107/S1600536807062927 ]

Dichlorido[1-(1-naphthylmethyl)-3-(2-pyridyl)-1H-pyrazole-[kappa]2N2,N3]palladium(II)

C.-S. Liu, G.-H. Sun and L.-Q. Guo

Abstract top

In the title compound, [PdCl2(C19H15N3)], the PdII 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 PdII mononuclear units form intermolecular C-H...[pi] interactions involving the benzene and pyridine rings of different L ligands and [pi]-[pi] stacking interactions between the pyrazolyl-pyridine and naphthalene rings of neighbouring L ligands, with a centroid-centroid separation of 3.522 (1) Å.

Comment top

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 PdII centre is four-coordinated by two N-atom donors from one L ligand and two Cl atoms. The coordination geometry around the PdII center can be described as a slightly distorted square-plane (Fig. 1). In the crystal structure, the PdII 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).

Related literature top

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). Cg1 is the centroid of atoms C1–C5/C10 and Cg2 is the centroid of atoms Pd1/N2/C14/C15/N3.

Experimental top

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%.

Refinement top

H atoms were included in calculated positions and treated in the subsequent refinement as riding atoms, with C—H = 0.93 (aromatic) or 0.97 Å (methylene), with Uiso(H) = 1.2 or 1.5 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998; 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 (Bruker, 199 and PLATON (Spek, 2003).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level for non-H atoms.
[Figure 2] Fig. 2. Part of the crystal packing showing a two-dimensional network structure in the title compound formed by the co-effects of intermolecular C—H···π (dashed solid lines) and π···π stacking (dashed open lines) interactions. For the sake of clarity, only H atoms involved in the interactions are shown.
Dichlorido[1-(1-naphthylmethyl)-3-(2-pyridyl)-1H-pyrazole- κ2N2,N3]palladium(II) top
Crystal data top
[PdCl2(C19H15N3)]F000 = 920
Mr = 462.64Dx = 1.705 Mg m−3
Orthorhombic, P212121Mo Kα radiation
λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 970 reflections
a = 9.330 (6) Åθ = 3.4–26.4º
b = 12.139 (8) ŵ = 1.33 mm−1
c = 15.918 (11) ÅT = 293 (2) K
V = 1803 (2) Å3Block, yellow
Z = 40.20 × 0.16 × 0.12 mm
Data collection top
Bruker SMART CCD
diffractometer		3702 independent reflections
Radiation source: fine-focus sealed tube3340 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.028
T = 293(2) Kθmax = 26.5º
ω scansθmin = 2.5º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −10→11
Tmin = 0.772, Tmax = 0.848k = −14→15
10453 measured reflectionsl = −19→15
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.024  w = 1/[σ2(Fo2) + (0.0227P)2 + 0.3859P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.054(Δ/σ)max = 0.001
S = 1.03Δρmax = 0.27 e Å−3
3702 reflectionsΔρmin = −0.37 e Å−3
226 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1580 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.00 (3)
Crystal data top
[PdCl2(C19H15N3)]V = 1803 (2) Å3
Mr = 462.64Z = 4
Orthorhombic, P212121Mo Kα
a = 9.330 (6) ŵ = 1.33 mm−1
b = 12.139 (8) ÅT = 293 (2) K
c = 15.918 (11) Å0.20 × 0.16 × 0.12 mm
Data collection top
Bruker SMART CCD
diffractometer		3702 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		3340 reflections with I > 2σ(I)
Tmin = 0.772, Tmax = 0.848Rint = 0.028
10453 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.024H-atom parameters constrained
wR(F2) = 0.054Δρmax = 0.27 e Å−3
S = 1.03Δρmin = −0.37 e Å−3
3702 reflectionsAbsolute structure: Flack (1983), 1580 Friedel pairs
226 parametersFlack parameter: 0.00 (3)
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) top
xyzUiso*/Ueq
Pd10.83064 (2)0.490954 (17)0.051890 (13)0.03837 (7)
C10.5698 (4)0.9043 (3)0.1086 (3)0.0546 (9)
H1A0.63810.90010.06620.065*
C20.5637 (4)0.9961 (3)0.1585 (3)0.0654 (10)
H2A0.62811.05340.14980.079*
C30.4620 (4)1.0044 (4)0.2221 (2)0.0704 (12)
H3A0.45891.06700.25570.084*
C40.3679 (4)0.9219 (4)0.2351 (2)0.0651 (11)
H4A0.29930.92900.27710.078*
C50.3714 (3)0.8245 (3)0.1859 (2)0.0511 (9)
C60.2756 (4)0.7376 (4)0.1995 (2)0.0639 (11)
H6A0.20780.74330.24210.077*
C70.2800 (4)0.6453 (3)0.1516 (3)0.0613 (10)
H7A0.21680.58780.16220.074*
C80.3806 (4)0.6365 (3)0.0856 (2)0.0505 (8)
H8A0.38240.57300.05300.061*
C90.4752 (3)0.7192 (2)0.0689 (2)0.0408 (7)
C100.4739 (3)0.8161 (3)0.1208 (2)0.0430 (7)
C110.5803 (3)0.7164 (2)−0.0027 (2)0.0444 (8)
H11A0.55760.7758−0.04120.053*
H11B0.67560.73010.01930.053*
C120.5032 (4)0.5886 (3)−0.1173 (2)0.0534 (8)
H12A0.43230.6329−0.14060.064*
C130.5448 (3)0.4872 (3)−0.1465 (2)0.0512 (8)
H13A0.50900.4492−0.19270.061*
C140.6522 (3)0.4540 (2)−0.09185 (19)0.0397 (7)
C150.7469 (3)0.3595 (2)−0.0911 (2)0.0394 (7)
C160.7465 (4)0.2785 (3)−0.1518 (2)0.0479 (8)
H16A0.67990.2806−0.19520.058*
C170.8446 (4)0.1953 (3)−0.1477 (3)0.0612 (10)
H17A0.84590.1404−0.18850.073*
C180.9416 (5)0.1935 (3)−0.0826 (3)0.0675 (13)
H18A1.00960.1377−0.07890.081*
C190.9366 (4)0.2753 (3)−0.0231 (3)0.0619 (11)
H19A1.00220.27400.02090.074*
N10.5823 (3)0.6132 (2)−0.04930 (19)0.0434 (6)
N20.6739 (3)0.53078 (17)−0.03249 (14)0.0378 (5)
N30.8397 (3)0.35759 (19)−0.02653 (16)0.0438 (6)
Cl11.00048 (11)0.42155 (9)0.13879 (7)0.0708 (3)
Cl20.81909 (11)0.64162 (6)0.13707 (5)0.0521 (2)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.03920 (11)0.03896 (11)0.03696 (11)0.00037 (11)0.00213 (10)0.00045 (11)
C10.058 (2)0.0449 (19)0.060 (2)0.0110 (17)−0.0040 (18)0.0000 (17)
C20.075 (2)0.0455 (19)0.076 (3)0.013 (2)−0.024 (2)−0.010 (2)
C30.077 (3)0.066 (3)0.068 (2)0.035 (3)−0.030 (2)−0.022 (2)
C40.062 (3)0.083 (3)0.051 (2)0.038 (2)−0.0089 (18)−0.015 (2)
C50.043 (2)0.064 (2)0.045 (2)0.0218 (16)−0.0049 (15)0.0039 (17)
C60.054 (2)0.091 (3)0.047 (2)0.019 (2)0.0085 (18)0.009 (2)
C70.052 (2)0.067 (3)0.065 (3)−0.0033 (18)0.0031 (19)0.016 (2)
C80.0479 (19)0.0458 (18)0.058 (2)0.0036 (15)−0.0020 (16)0.0069 (16)
C90.0423 (17)0.0381 (15)0.0422 (19)0.0102 (13)0.0011 (15)0.0071 (13)
C100.0429 (18)0.0443 (17)0.0417 (18)0.0133 (14)−0.0067 (14)−0.0004 (14)
C110.0485 (19)0.0372 (17)0.048 (2)0.0078 (15)0.0034 (15)0.0021 (16)
C120.056 (2)0.060 (2)0.045 (2)0.0141 (18)−0.0071 (18)0.0007 (16)
C130.0554 (18)0.057 (2)0.0416 (17)0.0038 (19)−0.0077 (14)−0.0047 (18)
C140.0411 (17)0.0422 (15)0.0357 (16)−0.0023 (14)0.0045 (14)0.0002 (12)
C150.0440 (18)0.0360 (16)0.0381 (18)−0.0043 (14)0.0079 (14)0.0011 (13)
C160.058 (2)0.0444 (19)0.041 (2)−0.0048 (15)0.0079 (16)−0.0053 (15)
C170.075 (3)0.0427 (18)0.065 (2)0.005 (2)0.015 (3)−0.0149 (16)
C180.074 (3)0.055 (2)0.073 (3)0.022 (2)−0.002 (2)−0.013 (2)
C190.070 (3)0.054 (2)0.062 (3)0.0214 (19)−0.011 (2)−0.0067 (17)
N10.0465 (15)0.0424 (13)0.0414 (15)0.0105 (11)0.0035 (13)0.0016 (14)
N20.0408 (12)0.0366 (11)0.0361 (13)0.0021 (11)0.0040 (11)0.0018 (9)
N30.0489 (15)0.0385 (12)0.0440 (15)0.0071 (14)0.0022 (14)0.0013 (10)
Cl10.0659 (6)0.0788 (6)0.0677 (6)0.0211 (5)−0.0224 (5)−0.0102 (5)
Cl20.0678 (5)0.0452 (4)0.0435 (4)−0.0047 (4)0.0009 (5)−0.0056 (3)
Geometric parameters (Å, °) top
Pd1—N22.043 (3)C9—C111.504 (5)
Pd1—N32.046 (3)C11—N11.456 (4)
Pd1—Cl12.2658 (14)C11—H11A0.970
Pd1—Cl22.2792 (14)C11—H11B0.970
C1—C21.370 (5)C12—N11.343 (5)
C1—C101.408 (5)C12—C131.372 (5)
C1—H1A0.930C12—H12A0.930
C2—C31.390 (6)C13—C141.387 (4)
C2—H2A0.930C13—H13A0.930
C3—C41.347 (6)C14—N21.342 (4)
C3—H3A0.930C14—C151.448 (4)
C4—C51.418 (5)C15—N31.343 (4)
C4—H4A0.930C15—C161.379 (4)
C5—C61.399 (5)C16—C171.365 (5)
C5—C101.414 (5)C16—H16A0.930
C6—C71.356 (6)C17—C181.377 (6)
C6—H6A0.930C17—H17A0.930
C7—C81.413 (5)C18—C191.373 (5)
C7—H7A0.930C18—H18A0.930
C8—C91.363 (5)C19—N31.348 (4)
C8—H8A0.930C19—H19A0.930
C9—C101.438 (4)N1—N21.343 (3)
N2—Pd1—N379.38 (10)C9—C11—H11A108.7
N2—Pd1—Cl1171.74 (7)N1—C11—H11B108.7
N3—Pd1—Cl192.83 (9)C9—C11—H11B108.7
N2—Pd1—Cl299.63 (7)H11A—C11—H11B107.6
N3—Pd1—Cl2178.86 (7)N1—C12—C13108.5 (3)
Cl1—Pd1—Cl288.18 (5)N1—C12—H12A125.8
C2—C1—C10120.8 (4)C13—C12—H12A125.8
C2—C1—H1A119.6C12—C13—C14104.6 (3)
C10—C1—H1A119.6C12—C13—H13A127.7
C1—C2—C3120.6 (4)C14—C13—H13A127.7
C1—C2—H2A119.7N2—C14—C13110.4 (3)
C3—C2—H2A119.7N2—C14—C15116.8 (3)
C4—C3—C2120.2 (4)C13—C14—C15132.6 (3)
C4—C3—H3A119.9N3—C15—C16121.7 (3)
C2—C3—H3A119.9N3—C15—C14114.4 (3)
C3—C4—C5121.3 (4)C16—C15—C14123.9 (3)
C3—C4—H4A119.3C17—C16—C15119.5 (4)
C5—C4—H4A119.3C17—C16—H16A120.2
C6—C5—C10119.4 (3)C15—C16—H16A120.2
C6—C5—C4121.9 (4)C16—C17—C18119.2 (3)
C10—C5—C4118.6 (4)C16—C17—H17A120.4
C7—C6—C5121.1 (4)C18—C17—H17A120.4
C7—C6—H6A119.5C19—C18—C17119.1 (4)
C5—C6—H6A119.5C19—C18—H18A120.5
C6—C7—C8120.1 (4)C17—C18—H18A120.5
C6—C7—H7A120.0N3—C19—C18122.0 (4)
C8—C7—H7A120.0N3—C19—H19A119.0
C9—C8—C7121.3 (3)C18—C19—H19A119.0
C9—C8—H8A119.4C12—N1—N2110.2 (3)
C7—C8—H8A119.4C12—N1—C11126.5 (3)
C8—C9—C10119.0 (3)N2—N1—C11123.2 (3)
C8—C9—C11123.6 (3)C14—N2—N1106.3 (2)
C10—C9—C11117.3 (3)C14—N2—Pd1113.99 (19)
C1—C10—C5118.5 (3)N1—N2—Pd1139.7 (2)
C1—C10—C9122.5 (3)C15—N3—C19118.4 (3)
C5—C10—C9119.1 (3)C15—N3—Pd1115.2 (2)
N1—C11—C9114.4 (3)C19—N3—Pd1126.1 (2)
N1—C11—H11A108.7
C10—C1—C2—C3−0.3 (5)C14—C15—C16—C17176.9 (3)
C1—C2—C3—C4−0.2 (6)C15—C16—C17—C180.4 (6)
C2—C3—C4—C51.1 (6)C16—C17—C18—C190.3 (6)
C3—C4—C5—C6179.1 (3)C17—C18—C19—N3−0.1 (7)
C3—C4—C5—C10−1.6 (5)C13—C12—N1—N2−0.4 (4)
C10—C5—C6—C70.4 (5)C13—C12—N1—C11175.1 (3)
C4—C5—C6—C7179.6 (4)C9—C11—N1—C1290.9 (4)
C5—C6—C7—C8−1.2 (6)C9—C11—N1—N2−94.1 (3)
C6—C7—C8—C90.4 (6)C13—C14—N2—N1−0.6 (3)
C7—C8—C9—C101.3 (5)C15—C14—N2—N1175.4 (2)
C7—C8—C9—C11−177.3 (3)C13—C14—N2—Pd1−179.9 (2)
C2—C1—C10—C5−0.2 (5)C15—C14—N2—Pd1−3.9 (3)
C2—C1—C10—C9178.9 (3)C12—N1—N2—C140.6 (3)
C6—C5—C10—C1−179.6 (3)C11—N1—N2—C14−175.1 (3)
C4—C5—C10—C11.1 (5)C12—N1—N2—Pd1179.6 (2)
C6—C5—C10—C91.3 (5)C11—N1—N2—Pd14.0 (5)
C4—C5—C10—C9−178.0 (3)N3—Pd1—N2—C142.0 (2)
C8—C9—C10—C1178.8 (3)Cl2—Pd1—N2—C14−178.62 (19)
C11—C9—C10—C1−2.5 (5)N3—Pd1—N2—N1−177.0 (3)
C8—C9—C10—C5−2.1 (5)Cl2—Pd1—N2—N12.4 (3)
C11—C9—C10—C5176.6 (3)C16—C15—N3—C191.7 (5)
C8—C9—C11—N1−5.1 (5)C14—C15—N3—C19−176.8 (3)
C10—C9—C11—N1176.2 (3)C16—C15—N3—Pd1176.1 (2)
N1—C12—C13—C140.0 (4)C14—C15—N3—Pd1−2.4 (3)
C12—C13—C14—N20.3 (4)C18—C19—N3—C15−0.9 (6)
C12—C13—C14—C15−174.8 (3)C18—C19—N3—Pd1−174.7 (3)
N2—C14—C15—N34.2 (4)N2—Pd1—N3—C150.3 (2)
C13—C14—C15—N3179.2 (3)Cl1—Pd1—N3—C15177.6 (2)
N2—C14—C15—C16−174.3 (3)N2—Pd1—N3—C19174.2 (3)
C13—C14—C15—C160.7 (6)Cl1—Pd1—N3—C19−8.5 (3)
N3—C15—C16—C17−1.5 (5)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C17—H17A···Cg1i0.932.893.602134
C18—H18A···Cg2ii0.933.053.803139
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1/2, −y+1/2, −z.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C17—H17A···Cg1i0.932.893.602134
C18—H18A···Cg2ii0.933.053.803139
Symmetry codes: (i) −x+3/2, −y+1, z−1/2; (ii) x+1/2, −y+1/2, −z.
Acknowledgements top

The authors thank Zhengzhou University of Light Industry and Henan Provincial Key Laboratory of Surface & Interface Science as well as Nankai University for supporting this work.

references
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