[1-Benzyl-3-(2-pyrid­yl)-1H-pyrazole-κ²N²,N³]dichloridopalladium(II)

In the title compound, [PdCl₂(C₁₅H₁₃N₃)], the Pd^II 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 Pd^II mononuclear units are linked to form dimers through C—H...π inter­actions. The dimers are further inter­linked by weak inter­molecular C—H...Cl inter­actions.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.029
• wR factor = 0.091
• Data-to-parameter ratio = 16.6

checkCIF/PLATON results

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Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K
PLAT794_ALERT_5_G Check Predicted Bond Valency for Pd1         (2)       2.10

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   0 ALERT level C = Check and explain
   3 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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S1. Comment

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

In the crystal structure, the Pd^II 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

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).

S2. Experimental

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%.

S3. Refinement

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 U_iso(H) = 1.2U_eq(C) and 1.5U_eq(O).

Computing details

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

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)

Crystal data

[PdCl2(C15H13N3)]	F(000) = 1632
Mr = 412.58	Dx = 1.772 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 831 reflections
a = 19.965 (6) Å	θ = 2.7–26.4°
b = 8.958 (3) Å	µ = 1.54 mm^−1
c = 17.482 (6) Å	T = 293 K
β = 98.356 (5)°	Block, yellow
V = 3093.4 (17) Å^3	0.19 × 0.15 × 0.11 mm
Z = 8

Data collection

Bruker SMART CCD area-detector diffractometer	3163 independent reflections
Radiation source: fine-focus sealed tube	2508 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.034
ϕ and ω scans	θmax = 26.4°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −23→24
Tmin = 0.759, Tmax = 0.849	k = −11→11
8670 measured reflections	l = −15→21

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.091	H-atom parameters constrained
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0537P)^2] where P = (Fo^2 + 2Fc^2)/3
3163 reflections	(Δ/σ)max = 0.001
190 parameters	Δρmax = 0.44 e Å^−3
0 restraints	Δρmin = −0.49 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Pd1	0.420580 (14)	0.88810 (3)	0.548219 (17)	0.02885 (12)
C1	0.29531 (19)	0.7276 (4)	0.3303 (2)	0.0326 (9)
C2	0.2583 (2)	0.6509 (5)	0.2711 (3)	0.0488 (12)
H2A	0.2230	0.5893	0.2808	0.059*
C3	0.2736 (3)	0.6651 (7)	0.1953 (3)	0.0655 (15)
H3A	0.2483	0.6133	0.1548	0.079*
C4	0.3257 (3)	0.7553 (5)	0.1814 (3)	0.0588 (14)
H4A	0.3357	0.7655	0.1314	0.071*
C5	0.3630 (3)	0.8305 (5)	0.2408 (3)	0.0540 (12)
H5A	0.3986	0.8911	0.2312	0.065*
C6	0.3481 (2)	0.8170 (5)	0.3150 (2)	0.0413 (10)
H6A	0.3738	0.8686	0.3552	0.050*
C7	0.27897 (19)	0.7142 (5)	0.4114 (2)	0.0360 (9)
H7A	0.2769	0.8133	0.4333	0.043*
H7B	0.2347	0.6686	0.4098	0.043*
C8	0.3326 (2)	0.4749 (4)	0.4638 (2)	0.0403 (10)
H8A	0.3025	0.4099	0.4350	0.048*
C9	0.3871 (2)	0.4338 (4)	0.5144 (2)	0.0411 (10)
H9A	0.4016	0.3373	0.5274	0.049*
C10	0.41689 (19)	0.5672 (4)	0.5427 (2)	0.0321 (9)
C11	0.4763 (2)	0.6006 (4)	0.5991 (2)	0.0328 (9)
C12	0.5161 (2)	0.4936 (5)	0.6407 (3)	0.0456 (11)
H12A	0.5059	0.3929	0.6332	0.055*
C13	0.5704 (2)	0.5360 (5)	0.6926 (3)	0.0519 (12)
H13A	0.5969	0.4649	0.7215	0.062*
C14	0.5853 (2)	0.6851 (6)	0.7015 (3)	0.0602 (14)
H14A	0.6227	0.7163	0.7357	0.072*
C15	0.5440 (2)	0.7882 (5)	0.6588 (3)	0.0554 (13)
H15A	0.5541	0.8891	0.6653	0.066*
N1	0.32876 (16)	0.6254 (3)	0.46161 (18)	0.0330 (7)
N2	0.38106 (15)	0.6844 (3)	0.51007 (17)	0.0284 (7)
N3	0.49013 (16)	0.7480 (4)	0.60870 (19)	0.0352 (8)
Cl1	0.33790 (5)	1.04250 (11)	0.48807 (6)	0.0442 (3)
Cl2	0.47619 (5)	1.09442 (11)	0.59927 (7)	0.0451 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Pd1	0.03081 (18)	0.02245 (16)	0.03280 (18)	−0.00040 (12)	0.00294 (12)	0.00010 (12)
C1	0.032 (2)	0.031 (2)	0.033 (2)	0.0043 (16)	−0.0004 (17)	−0.0011 (16)
C2	0.043 (3)	0.056 (3)	0.044 (3)	−0.008 (2)	−0.006 (2)	0.000 (2)
C3	0.070 (4)	0.080 (4)	0.039 (3)	0.011 (3)	−0.016 (3)	−0.013 (3)
C4	0.084 (4)	0.062 (3)	0.032 (2)	0.028 (3)	0.011 (3)	0.008 (2)
C5	0.070 (3)	0.044 (3)	0.053 (3)	0.003 (2)	0.025 (3)	0.006 (2)
C6	0.046 (2)	0.040 (2)	0.039 (2)	−0.004 (2)	0.010 (2)	−0.0039 (19)
C7	0.029 (2)	0.042 (2)	0.037 (2)	−0.0048 (17)	0.0017 (17)	−0.0012 (18)
C8	0.051 (3)	0.031 (2)	0.037 (2)	−0.0148 (19)	0.002 (2)	−0.0025 (18)
C9	0.058 (3)	0.026 (2)	0.040 (2)	−0.0046 (19)	0.006 (2)	0.0003 (18)
C10	0.039 (2)	0.0260 (18)	0.031 (2)	−0.0008 (17)	0.0058 (18)	0.0038 (16)
C11	0.038 (2)	0.028 (2)	0.033 (2)	0.0037 (17)	0.0070 (18)	0.0014 (17)
C12	0.054 (3)	0.034 (2)	0.048 (3)	0.006 (2)	0.005 (2)	0.004 (2)
C13	0.046 (3)	0.051 (3)	0.056 (3)	0.018 (2)	−0.003 (2)	0.012 (2)
C14	0.042 (3)	0.058 (3)	0.073 (3)	0.006 (2)	−0.017 (3)	0.004 (3)
C15	0.045 (3)	0.042 (3)	0.074 (3)	−0.006 (2)	−0.010 (2)	−0.003 (2)
N1	0.0356 (18)	0.0317 (18)	0.0306 (17)	−0.0065 (14)	0.0011 (14)	0.0006 (14)
N2	0.0304 (16)	0.0243 (16)	0.0299 (16)	−0.0011 (14)	0.0025 (14)	0.0011 (13)
N3	0.0330 (18)	0.0292 (17)	0.0414 (19)	0.0007 (14)	−0.0017 (15)	0.0014 (14)
Cl1	0.0472 (6)	0.0307 (5)	0.0503 (6)	0.0081 (5)	−0.0079 (5)	−0.0003 (5)
Cl2	0.0428 (6)	0.0265 (5)	0.0632 (7)	−0.0029 (4)	−0.0012 (5)	−0.0093 (5)

Geometric parameters (Å, º)

Pd1—N3	2.048 (3)	C8—C9	1.349 (6)
Pd1—N2	2.060 (3)	C8—N1	1.350 (5)
Pd1—Cl2	2.2709 (11)	C8—H8A	0.9300
Pd1—Cl1	2.2889 (11)	C9—C10	1.393 (5)
C1—C2	1.367 (5)	C9—H9A	0.9300
C1—C6	1.380 (6)	C10—N2	1.349 (5)
C1—C7	1.506 (5)	C10—C11	1.460 (5)
C2—C3	1.408 (7)	C11—N3	1.354 (5)
C2—H2A	0.9300	C11—C12	1.382 (5)
C3—C4	1.366 (7)	C12—C13	1.362 (6)
C3—H3A	0.9300	C12—H12A	0.9300
C4—C5	1.364 (7)	C13—C14	1.372 (7)
C4—H4A	0.9300	C13—H13A	0.9300
C5—C6	1.377 (6)	C14—C15	1.382 (6)
C5—H5A	0.9300	C14—H14A	0.9300
C6—H6A	0.9300	C15—N3	1.334 (5)
C7—N1	1.462 (5)	C15—H15A	0.9300
C7—H7A	0.9700	N1—N2	1.353 (4)
C7—H7B	0.9700
N3—Pd1—N2	79.81 (12)	N1—C8—H8A	125.4
N3—Pd1—Cl2	92.28 (10)	C8—C9—C10	105.2 (4)
N2—Pd1—Cl2	172.08 (9)	C8—C9—H9A	127.4
N3—Pd1—Cl1	175.60 (10)	C10—C9—H9A	127.4
N2—Pd1—Cl1	99.78 (9)	N2—C10—C9	110.1 (3)
Cl2—Pd1—Cl1	88.14 (4)	N2—C10—C11	117.1 (3)
C2—C1—C6	119.3 (4)	C9—C10—C11	132.8 (4)
C2—C1—C7	120.4 (4)	N3—C11—C12	121.3 (4)
C6—C1—C7	120.3 (3)	N3—C11—C10	114.5 (3)
C1—C2—C3	120.0 (4)	C12—C11—C10	124.2 (4)
C1—C2—H2A	120.0	C13—C12—C11	119.9 (4)
C3—C2—H2A	120.0	C13—C12—H12A	120.1
C4—C3—C2	119.7 (5)	C11—C12—H12A	120.1
C4—C3—H3A	120.2	C12—C13—C14	119.0 (4)
C2—C3—H3A	120.2	C12—C13—H13A	120.5
C5—C4—C3	120.2 (5)	C14—C13—H13A	120.5
C5—C4—H4A	119.9	C13—C14—C15	119.1 (4)
C3—C4—H4A	119.9	C13—C14—H14A	120.4
C4—C5—C6	120.3 (5)	C15—C14—H14A	120.4
C4—C5—H5A	119.8	N3—C15—C14	122.3 (4)
C6—C5—H5A	119.8	N3—C15—H15A	118.8
C5—C6—C1	120.5 (4)	C14—C15—H15A	118.8
C5—C6—H6A	119.7	C8—N1—N2	109.7 (3)
C1—C6—H6A	119.7	C8—N1—C7	126.2 (3)
N1—C7—C1	112.8 (3)	N2—N1—C7	124.0 (3)
N1—C7—H7A	109.0	C10—N2—N1	105.9 (3)
C1—C7—H7A	109.0	C10—N2—Pd1	113.4 (2)
N1—C7—H7B	109.0	N1—N2—Pd1	140.6 (2)
C1—C7—H7B	109.0	C15—N3—C11	118.3 (4)
H7A—C7—H7B	107.8	C15—N3—Pd1	126.5 (3)
C9—C8—N1	109.1 (3)	C11—N3—Pd1	115.0 (3)
C9—C8—H8A	125.4
C6—C1—C2—C3	−0.8 (7)	C1—C7—N1—C8	−79.0 (5)
C7—C1—C2—C3	179.4 (4)	C1—C7—N1—N2	96.7 (4)
C1—C2—C3—C4	0.3 (8)	C9—C10—N2—N1	0.3 (4)
C2—C3—C4—C5	0.4 (8)	C11—C10—N2—N1	−179.1 (3)
C3—C4—C5—C6	−0.5 (7)	C9—C10—N2—Pd1	179.8 (3)
C4—C5—C6—C1	−0.1 (7)	C11—C10—N2—Pd1	0.5 (4)
C2—C1—C6—C5	0.7 (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—N1	106.9 (4)	C8—N1—N2—Pd1	−179.9 (3)
C6—C1—C7—N1	−72.8 (5)	C7—N1—N2—Pd1	3.7 (6)
N1—C8—C9—C10	−0.5 (5)	N3—Pd1—N2—C10	1.4 (3)
C8—C9—C10—N2	0.1 (5)	Cl1—Pd1—N2—C10	−174.1 (2)
C8—C9—C10—C11	179.3 (4)	N3—Pd1—N2—N1	−179.2 (4)
N2—C10—C11—N3	−3.3 (5)	Cl1—Pd1—N2—N1	5.2 (4)
C9—C10—C11—N3	177.6 (4)	C14—C15—N3—C11	−0.7 (7)
N2—C10—C11—C12	176.4 (4)	C14—C15—N3—Pd1	174.9 (4)
C9—C10—C11—C12	−2.8 (7)	C12—C11—N3—C15	0.9 (6)
N3—C11—C12—C13	0.2 (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—Pd1	4.5 (4)
C12—C13—C14—C15	1.4 (8)	N2—Pd1—N3—C15	−179.0 (4)
C13—C14—C15—N3	−0.4 (8)	Cl2—Pd1—N3—C15	1.6 (4)
C9—C8—N1—N2	0.7 (5)	N2—Pd1—N3—C11	−3.3 (3)
C9—C8—N1—C7	176.9 (3)	Cl2—Pd1—N3—C11	177.3 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13A···Cg1^i	0.93	2.60	3.4635	155
C9—H9A···Cl2^ii	0.93	2.83	3.721 (5)	162
C12—H12A···Cl2^ii	0.93	2.78	3.712 (5)	176

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x, y−1, z.