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Acta Cryst. (2007). E63, m2892    [ doi:10.1107/S1600536807054049 ]

[1-Benzyl-3-(2-pyridyl)-1H-pyrazole-[kappa]2N2,N3]dichloridopalladium(II)

C.-S. Liu and X.-S. Shi

Abstract top

In the title compound, [PdCl2(C15H13N3)], the PdII center is four-coordinated by two N-atom donors from one 1-benzyl-3-(2-pyridyl)-1H-pyrazole ligand and by two Cl atoms in a distorted square-planar coordination environment. In the crystal structure, adjacent PdII mononuclear units are linked to form dimers through C-H...[pi] interactions. The dimers are further interlinked by weak intermolecular C-H...Cl interactions.

Comment top

Nowadays, much 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 many 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) have been reported. Recently, we have reported the preparation of a non-planar ligand, 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]benzene (denoted L) (Liu et al., 2007; Shi et al., 2005). Now we report here the crystal structure of a palladium complex of this ligand, [Pd(L)Cl2].

In the title compound, the PdII center is four-coordinated by two N-atoms from one L ligand and two Cl atoms (Table 1). The coordination geometry around the PdII center can be described as distorted square planar (Fig. 1).

In the crystal structure, the PdII mononuclear units at (x, y, z) and (1 − x, 2 − y, −z) are interconnected to form a dimer through intermolecular C—H···π interactions involving C1—C6 (centroid Cg1) benzene rings of the L ligands (Sony and Ponnuswamy, 2006) (Table 2). The dimers are further interlinked to form a chain along the b axis by weak intermolecular C—H···Cl (Table 2) interactions (Desiraju & Steiner, 1999).

Related literature top

For related literature, see: Bell et al. (2003); Desiraju & Steiner (1999); Liu et al. (2007); Paul et al. (2004); Shi et al. (2005); Sony & Ponnuswamy (2006); Steel (2005); Ward et al. (2001); Singh et al. (2003); Zou et al. (2004).

Experimental top

The ligand 1-[3-(2-pyridyl)pyrazol-1-ylmethyl]benzene (L) was synthesized according to the method reported in the literature (Liu et al., 2007; Shi et al., 2005). A solution of PdCl2 (0.1 mmol) in the mixture solution of 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: ~30%). Analysis calculated for (C15H13PdCl2N2): C 45.20, H 3.29, N 7.03%; found: C 45.11, H 3.41, N 7.21%.

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) and O—H = 0.82 Å, and with Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
[1-Benzyl-3-(2-pyridyl)-1H-pyrazole- κ2N2,N3]dichloridopalladium(II) top
Crystal data top
[PdCl2(C15H13N3)]F000 = 1632
Mr = 412.58Dx = 1.772 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 831 reflections
a = 19.965 (6) Åθ = 2.7–26.4º
b = 8.958 (3) ŵ = 1.54 mm−1
c = 17.482 (6) ÅT = 293 (2) K
β = 98.356 (5)ºBlock, yellow
V = 3093.4 (17) Å30.19 × 0.15 × 0.11 mm
Z = 8
Data collection top
Bruker SMART CCD area-detector
diffractometer		3163 independent reflections
Radiation source: fine-focus sealed tube2508 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.034
T = 293(2) Kθmax = 26.4º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		h = −23→24
Tmin = 0.759, Tmax = 0.849k = −11→11
8670 measured reflectionsl = −15→21
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.091  w = 1/[σ2(Fo2) + (0.0537P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
3163 reflectionsΔρmax = 0.44 e Å−3
190 parametersΔρmin = −0.49 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[PdCl2(C15H13N3)]V = 3093.4 (17) Å3
Mr = 412.58Z = 8
Monoclinic, C2/cMo Kα
a = 19.965 (6) ŵ = 1.54 mm−1
b = 8.958 (3) ÅT = 293 (2) K
c = 17.482 (6) Å0.19 × 0.15 × 0.11 mm
β = 98.356 (5)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3163 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1998)		2508 reflections with I > 2σ(I)
Tmin = 0.759, Tmax = 0.849Rint = 0.034
8670 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029190 parameters
wR(F2) = 0.091H-atom parameters constrained
S = 1.02Δρmax = 0.44 e Å−3
3163 reflectionsΔρmin = −0.49 e Å−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
Pd10.420580 (14)0.88810 (3)0.548219 (17)0.02885 (12)
C10.29531 (19)0.7276 (4)0.3303 (2)0.0326 (9)
C20.2583 (2)0.6509 (5)0.2711 (3)0.0488 (12)
H2A0.22300.58930.28080.059*
C30.2736 (3)0.6651 (7)0.1953 (3)0.0655 (15)
H3A0.24830.61330.15480.079*
C40.3257 (3)0.7553 (5)0.1814 (3)0.0588 (14)
H4A0.33570.76550.13140.071*
C50.3630 (3)0.8305 (5)0.2408 (3)0.0540 (12)
H5A0.39860.89110.23120.065*
C60.3481 (2)0.8170 (5)0.3150 (2)0.0413 (10)
H6A0.37380.86860.35520.050*
C70.27897 (19)0.7142 (5)0.4114 (2)0.0360 (9)
H7A0.27690.81330.43330.043*
H7B0.23470.66860.40980.043*
C80.3326 (2)0.4749 (4)0.4638 (2)0.0403 (10)
H8A0.30250.40990.43500.048*
C90.3871 (2)0.4338 (4)0.5144 (2)0.0411 (10)
H9A0.40160.33730.52740.049*
C100.41689 (19)0.5672 (4)0.5427 (2)0.0321 (9)
C110.4763 (2)0.6006 (4)0.5991 (2)0.0328 (9)
C120.5161 (2)0.4936 (5)0.6407 (3)0.0456 (11)
H12A0.50590.39290.63320.055*
C130.5704 (2)0.5360 (5)0.6926 (3)0.0519 (12)
H13A0.59690.46490.72150.062*
C140.5853 (2)0.6851 (6)0.7015 (3)0.0602 (14)
H14A0.62270.71630.73570.072*
C150.5440 (2)0.7882 (5)0.6588 (3)0.0554 (13)
H15A0.55410.88910.66530.066*
N10.32876 (16)0.6254 (3)0.46161 (18)0.0330 (7)
N20.38106 (15)0.6844 (3)0.51007 (17)0.0284 (7)
N30.49013 (16)0.7480 (4)0.60870 (19)0.0352 (8)
Cl10.33790 (5)1.04250 (11)0.48807 (6)0.0442 (3)
Cl20.47619 (5)1.09442 (11)0.59927 (7)0.0451 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Pd10.03081 (18)0.02245 (16)0.03280 (18)−0.00040 (12)0.00294 (12)0.00010 (12)
C10.032 (2)0.031 (2)0.033 (2)0.0043 (16)−0.0004 (17)−0.0011 (16)
C20.043 (3)0.056 (3)0.044 (3)−0.008 (2)−0.006 (2)0.000 (2)
C30.070 (4)0.080 (4)0.039 (3)0.011 (3)−0.016 (3)−0.013 (3)
C40.084 (4)0.062 (3)0.032 (2)0.028 (3)0.011 (3)0.008 (2)
C50.070 (3)0.044 (3)0.053 (3)0.003 (2)0.025 (3)0.006 (2)
C60.046 (2)0.040 (2)0.039 (2)−0.004 (2)0.010 (2)−0.0039 (19)
C70.029 (2)0.042 (2)0.037 (2)−0.0048 (17)0.0017 (17)−0.0012 (18)
C80.051 (3)0.031 (2)0.037 (2)−0.0148 (19)0.002 (2)−0.0025 (18)
C90.058 (3)0.026 (2)0.040 (2)−0.0046 (19)0.006 (2)0.0003 (18)
C100.039 (2)0.0260 (18)0.031 (2)−0.0008 (17)0.0058 (18)0.0038 (16)
C110.038 (2)0.028 (2)0.033 (2)0.0037 (17)0.0070 (18)0.0014 (17)
C120.054 (3)0.034 (2)0.048 (3)0.006 (2)0.005 (2)0.004 (2)
C130.046 (3)0.051 (3)0.056 (3)0.018 (2)−0.003 (2)0.012 (2)
C140.042 (3)0.058 (3)0.073 (3)0.006 (2)−0.017 (3)0.004 (3)
C150.045 (3)0.042 (3)0.074 (3)−0.006 (2)−0.010 (2)−0.003 (2)
N10.0356 (18)0.0317 (18)0.0306 (17)−0.0065 (14)0.0011 (14)0.0006 (14)
N20.0304 (16)0.0243 (16)0.0299 (16)−0.0011 (14)0.0025 (14)0.0011 (13)
N30.0330 (18)0.0292 (17)0.0414 (19)0.0007 (14)−0.0017 (15)0.0014 (14)
Cl10.0472 (6)0.0307 (5)0.0503 (6)0.0081 (5)−0.0079 (5)−0.0003 (5)
Cl20.0428 (6)0.0265 (5)0.0632 (7)−0.0029 (4)−0.0012 (5)−0.0093 (5)
Geometric parameters (Å, °) top
Pd1—N32.048 (3)C8—C91.349 (6)
Pd1—N22.060 (3)C8—N11.350 (5)
Pd1—Cl22.2709 (11)C8—H8A0.9300
Pd1—Cl12.2889 (11)C9—C101.393 (5)
C1—C21.367 (5)C9—H9A0.9300
C1—C61.380 (6)C10—N21.349 (5)
C1—C71.506 (5)C10—C111.460 (5)
C2—C31.408 (7)C11—N31.354 (5)
C2—H2A0.9300C11—C121.382 (5)
C3—C41.366 (7)C12—C131.362 (6)
C3—H3A0.9300C12—H12A0.9300
C4—C51.364 (7)C13—C141.372 (7)
C4—H4A0.9300C13—H13A0.9300
C5—C61.377 (6)C14—C151.382 (6)
C5—H5A0.9300C14—H14A0.9300
C6—H6A0.9300C15—N31.334 (5)
C7—N11.462 (5)C15—H15A0.9300
C7—H7A0.9700N1—N21.353 (4)
C7—H7B0.9700
N3—Pd1—N279.81 (12)N1—C8—H8A125.4
N3—Pd1—Cl292.28 (10)C8—C9—C10105.2 (4)
N2—Pd1—Cl2172.08 (9)C8—C9—H9A127.4
N3—Pd1—Cl1175.60 (10)C10—C9—H9A127.4
N2—Pd1—Cl199.78 (9)N2—C10—C9110.1 (3)
Cl2—Pd1—Cl188.14 (4)N2—C10—C11117.1 (3)
C2—C1—C6119.3 (4)C9—C10—C11132.8 (4)
C2—C1—C7120.4 (4)N3—C11—C12121.3 (4)
C6—C1—C7120.3 (3)N3—C11—C10114.5 (3)
C1—C2—C3120.0 (4)C12—C11—C10124.2 (4)
C1—C2—H2A120.0C13—C12—C11119.9 (4)
C3—C2—H2A120.0C13—C12—H12A120.1
C4—C3—C2119.7 (5)C11—C12—H12A120.1
C4—C3—H3A120.2C12—C13—C14119.0 (4)
C2—C3—H3A120.2C12—C13—H13A120.5
C5—C4—C3120.2 (5)C14—C13—H13A120.5
C5—C4—H4A119.9C13—C14—C15119.1 (4)
C3—C4—H4A119.9C13—C14—H14A120.4
C4—C5—C6120.3 (5)C15—C14—H14A120.4
C4—C5—H5A119.8N3—C15—C14122.3 (4)
C6—C5—H5A119.8N3—C15—H15A118.8
C5—C6—C1120.5 (4)C14—C15—H15A118.8
C5—C6—H6A119.7C8—N1—N2109.7 (3)
C1—C6—H6A119.7C8—N1—C7126.2 (3)
N1—C7—C1112.8 (3)N2—N1—C7124.0 (3)
N1—C7—H7A109.0C10—N2—N1105.9 (3)
C1—C7—H7A109.0C10—N2—Pd1113.4 (2)
N1—C7—H7B109.0N1—N2—Pd1140.6 (2)
C1—C7—H7B109.0C15—N3—C11118.3 (4)
H7A—C7—H7B107.8C15—N3—Pd1126.5 (3)
C9—C8—N1109.1 (3)C11—N3—Pd1115.0 (3)
C9—C8—H8A125.4
C6—C1—C2—C3−0.8 (7)C1—C7—N1—C8−79.0 (5)
C7—C1—C2—C3179.4 (4)C1—C7—N1—N296.7 (4)
C1—C2—C3—C40.3 (8)C9—C10—N2—N10.3 (4)
C2—C3—C4—C50.4 (8)C11—C10—N2—N1−179.1 (3)
C3—C4—C5—C6−0.5 (7)C9—C10—N2—Pd1179.8 (3)
C4—C5—C6—C1−0.1 (7)C11—C10—N2—Pd10.5 (4)
C2—C1—C6—C50.7 (6)C8—N1—N2—C10−0.6 (4)
C7—C1—C6—C5−179.5 (4)C7—N1—N2—C10−176.9 (3)
C2—C1—C7—N1106.9 (4)C8—N1—N2—Pd1−179.9 (3)
C6—C1—C7—N1−72.8 (5)C7—N1—N2—Pd13.7 (6)
N1—C8—C9—C10−0.5 (5)N3—Pd1—N2—C101.4 (3)
C8—C9—C10—N20.1 (5)Cl1—Pd1—N2—C10−174.1 (2)
C8—C9—C10—C11179.3 (4)N3—Pd1—N2—N1−179.2 (4)
N2—C10—C11—N3−3.3 (5)Cl1—Pd1—N2—N15.2 (4)
C9—C10—C11—N3177.6 (4)C14—C15—N3—C11−0.7 (7)
N2—C10—C11—C12176.4 (4)C14—C15—N3—Pd1174.9 (4)
C9—C10—C11—C12−2.8 (7)C12—C11—N3—C150.9 (6)
N3—C11—C12—C130.2 (6)C10—C11—N3—C15−179.5 (4)
C10—C11—C12—C13−179.5 (4)C12—C11—N3—Pd1−175.2 (3)
C11—C12—C13—C14−1.3 (7)C10—C11—N3—Pd14.5 (4)
C12—C13—C14—C151.4 (8)N2—Pd1—N3—C15−179.0 (4)
C13—C14—C15—N3−0.4 (8)Cl2—Pd1—N3—C151.6 (4)
C9—C8—N1—N20.7 (5)N2—Pd1—N3—C11−3.3 (3)
C9—C8—N1—C7176.9 (3)Cl2—Pd1—N3—C11177.3 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···Cg1i0.932.603.4635155
C9—H9A···Cl2ii0.932.833.721 (5)162
C12—H12A···Cl2ii0.932.783.712 (5)176
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y−1, z.
Table 1
Selected geometric parameters (Å, °) top
Pd1—N32.048 (3)Pd1—Cl22.2709 (11)
Pd1—N22.060 (3)Pd1—Cl12.2889 (11)
N3—Pd1—N279.81 (12)N3—Pd1—Cl1175.60 (10)
N3—Pd1—Cl292.28 (10)N2—Pd1—Cl199.78 (9)
N2—Pd1—Cl2172.08 (9)Cl2—Pd1—Cl188.14 (4)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C13—H13A···Cg1i0.932.603.4635155
C9—H9A···Cl2ii0.932.833.721 (5)162
C12—H12A···Cl2ii0.932.783.712 (5)176
Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y−1, 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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