Redetermination of (2,2′-bipyridine-κ2 N,N′)dichlorido­palladium(II) dichloro­methane solvate

Nam-Ho Kim; In-Chul Hwang; Kwang Ha

doi:10.1107/S1600536809016262

. 2009 May 7;65(Pt 6):m615–m616. doi: 10.1107/S1600536809016262

Redetermination of (2,2′-bipyridine-κ² N,N′)dichloridopalladium(II) dichloromethane solvate

Nam-Ho Kim ^a, In-Chul Hwang ^b, Kwang Ha ^a,^*

PMCID: PMC2969654 PMID: 21582986

Abstract

In the title compound, [PdCl₂(C₁₀H₈N₂)]·CH₂Cl₂, the Pd²⁺ ion is four-coordinated in a slightly distorted square-planar environment by two N atoms of the 2,2′-bipyridine (bipy) ligand and two chloride ions. The compound displays intramolecular C—H⋯Cl hydrogen bonds and pairs of complex molecules are connected by intermolecular C—H⋯Cl hydrogen bonds. Intermolecular π–π interactions are present between the pyridine rings of the ligand, the shortest centroid–centroid distance being 4.096 (3) Å. As a result of the electronic nature of the chelate ring, it is possible to create π–π interactions to its symmetry-related counterpart [3.720 (2) Å] and also with a pyridine ring [3.570 (3) Å] of the bipy unit. The present structure is a redetermination of a previous structure [Vicente et al. (1997 ▶). Private communication (refcode PYCXMN02). CCDC, Cambridge, England]. In the new structure refinement all H atoms were located in a difference Fourier synthesis. Their coordinates were refined freely, together with isotropic displacement parameters.

Related literature

For crystal structures of [PdX ₂(bipy)] (X = Cl or Br), see: Maekawa et al. (1991 ▶); Vicente et al. (1997 ▶); Smeets et al. (1997 ▶). For related Pt(II, IV)–bipyridine complexes, see: Osborn & Rogers (1974 ▶); Hambley (1986 ▶); Sartori et al. (2005 ▶); Momeni et al. (2007 ▶); Kim et al. (2009 ▶).

Experimental

Crystal data

[PdCl₂(C₁₀H₈N₂)]·CH₂Cl₂
M _r = 418.41
Triclinic,
a = 8.7913 (10) Å
b = 9.1115 (11) Å
c = 10.1846 (12) Å
α = 72.481 (2)°
β = 66.983 (2)°
γ = 81.429 (2)°
V = 715.58 (15) Å³
Z = 2
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 293 K
0.20 × 0.08 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.623, T _max = 0.850
4221 measured reflections
2862 independent reflections
2298 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.097
S = 1.05
2862 reflections
203 parameters
All H-atom parameters refined
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.69 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 datablocks global, I. DOI: 10.1107/S1600536809016262/kp2220sup1.cif

e-65-0m615-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016262/kp2220Isup2.hkl

e-65-0m615-Isup2.hkl^{(140.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pd1—N2	2.025 (4)
Pd1—N1	2.029 (4)
Pd1—Cl2	2.2853 (14)
Pd1—Cl1	2.2964 (14)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯Cl2	0.93 (5)	2.59 (5)	3.230 (6)	126 (4)
C2—H2⋯Cl2ⁱ	0.93 (5)	2.79 (5)	3.595 (7)	145 (4)
C10—H10⋯Cl1	0.86 (5)	2.68 (5)	3.248 (6)	125 (4)
C11—H11B⋯Cl1	0.99 (6)	2.63 (6)	3.578 (8)	161 (5)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Korea Research Foundation Grant funded by the Korean Government (MOEHRD) (KRF-2007–412-J02001).

supplementary crystallographic information

Comment

The asymmetric unit of the title compound, [PdCl₂(C₁₀H₈N₂)].CH₂Cl₂, contains a neutral Pd^II complex and a solvent molecule (Fig. 1). The compound crystallized in the triclinic space group P1, whereas the previously reported complex [PdCl₂(C₁₀H₈N₂)] crystallized in the orthorhombic space group C222₁ (Maekawa et al., 1991). The X-ray structure analysis of the title compound was previously carried out (Vicente et al., 1997) and the structure is stored in CCDC code: RAGVUQ. The stored and our crystal structures are in agreement, however, the new structure determination provides data on hydrogen bonding based on H atoms positions located from a difference Fourier synthesis and refined isotropically.

In the complex, the Pd²⁺ ion is four-coordinated in a distorted square-planar environment by two N atoms of the 2,2'-bipyridine (bipy) ligand and two Cl ions. The main contribution to the distortion is the tight N1—Pd1—N2 chelate angle (81.04 (16)°), which results in non-linear trans arrangement (<N1—Pd1—Cl1 = 175.78 (12)° and <N2—Pd1—Cl2 = 174.97 (12)°). The Pd1—N and Pd1—Cl bond lengths are almost equal (Pd1—N: 2.029 (4) and 2.025 (4) Å; Pd1—Cl 2.2964 (14) and 2.2853 (14) Å), respectively (Table 1), and close to those reported for [PdCl₂(C₁₀H₈N₂)] (Maekawa et al., 1991). The best least-squares plane of the atoms of the planar complex, except Cl2, reveals mean deviation of 0.026 (5) Å; deviation of Cl2 from this plane is 0.184 (2) Å. The compound displays the inter- and intramolecular C—H···Cl hydrogen bonds (Table 2) and molecules are connected by intermolecular hydrogen bonds and stacked in layres along the c axis (Fig. 2). Intermolecular π-π interactions (defined by separation distance between the ring centroids (the symmetry operation for second plane 1-x,1-y,-z) involve the planes: Pd1,N1→ N2 and ity symmetry related counterpart, 3.720 (2) Å, planes are parallel and shifted for 1.506 Å; Pd1,N1→ N2 and N1→ C5, 3.570 (3) Å, the dihedral angle between planes is 1.54 °, no shift; N1→ C5 and N2→ C10, 4.096 (3) Å the dihedral angle between planes is 2.72 °, no shift.

Experimental

To a solution of Na₂PdCl₄ (0.300 g, 1.020 mmol) in EtOH (30 ml) was added 2,2'-bipyridine (0.159 g, 1.018 mmol) and stirred for 5 h at room temperature. The precipitate obtained was separated by filtration and washed with EtOH and water and dried under vacuum, to give a yellow powder (0.302 g). Crystals suitable for X-ray analysis were obtained by slow evaporation from a CH₂Cl₂ solution.