(2,2′-Bi­pyridine-κ2 N,N′)di­chloridopalladium(II) 1,4-dioxane hemisolvate

Ricardo Alfredo Gutiérrez Márquez; Carmela Crisóstomo-Lucas; David Morales-Morales; Simón Hernández-Ortega

doi:10.1107/S1600536814009507

. 2014 May 17;70(Pt 6):m218. doi: 10.1107/S1600536814009507

(2,2′-Bipyridine-κ² N,N′)dichloridopalladium(II) 1,4-dioxane hemisolvate

Ricardo Alfredo Gutiérrez Márquez ^a, Carmela Crisóstomo-Lucas ^a,^*, David Morales-Morales ^a, Simón Hernández-Ortega ^a

PMCID: PMC4051027 PMID: 24940204

Abstract

The asymmetric unit of the title compound, [PdCl₂(C₁₀H₈N₂)]·0.5C₄H₈O₂, consists of one Pd^II complex molecule and a half-molecule of 1,4-dioxane, the complete molecule being generated by inversion symmetry. The Pd^II atom has an almost square-planar coordination formed by the 2,2′-bipyridine ligand and two chloride ligands. Two intramolecular C—H⋯Cl hydrogen bonds occur. In the crystal, the Pd^II complex and 1,4-dioxane molecules are connected by C—H⋯O hydrogen bonds, forming a layer parallel to (10-1). Within the layer, weak π–π interactions [centroid–centroid distance = 3.817 (4) Å] are observed between the pyridine rings.

Related literature

For related structures, see: Maekawa et al. (1991 ▶); Vicente et al. (1997 ▶); Kim et al. (2009 ▶). For palladium complexes with chelate ligands, see: Pointillart et al. (2007 ▶); Pazderski et al. (2006 ▶); Ferbinteanu et al. (1998 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

[PdCl(C₁₀H₈N₂)₂]·0.5C₄H₈O₂
M _r = 377.54
Monoclinic,
a = 7.2416 (5) Å
b = 14.6215 (10) Å
c = 12.9562 (9) Å
β = 105.423 (2)°
V = 1322.44 (16) Å³
Z = 4
Mo Kα radiation
μ = 1.80 mm⁻¹
T = 298 K
0.40 × 0.07 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.365, T _max = 0.906
7244 measured reflections
2414 independent reflections
1813 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.153
S = 1.03
2414 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 1.49 e Å⁻³
Δρ_min = −1.13 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_publ_block. DOI: 10.1107/S1600536814009507/is5358sup1.cif

e-70-0m218-sup1.cif^{(261.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009507/is5358Isup2.hkl

e-70-0m218-Isup2.hkl^{(132.8KB, hkl)}

CCDC reference: 999627

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1	0.93	2.55	3.471 (9)	170
C5—H5⋯O1ⁱ	0.93	2.57	3.464 (8)	163
C9—H9⋯O1	0.93	2.66	3.587 (8)	174
C6—H6⋯Cl2	0.93	2.65	3.239 (7)	122
C12—H12⋯Cl1	0.93	2.65	3.238 (7)	122

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Symmetry code: (i) Inline graphic .

supplementary crystallographic information

1. Comment

In recent years the use of chelate ligands of the type N—N has been of great interest due to the versatility of its applications. This is particularly true in the case of supramolecular chemistry and crystal engineering, where these kind of chelates are often used as blocking ligands and the study of their metallic derivatives in the solid state has revealed the tremendous importance of non-covalent interactions and advanced the understanding of the reactivity of these species (Pointillart et al., 2007; Pazderski et al., 2006). Complexes of group 10 elements with these ligands often present square planar geometries, and in some cases, they can exhibit interesting dimeric and trimeric structures (Ferbinteanu et al. 1998). The coordination complex [PdCl₂(C₁₀H₈N₂)] has been described before (Maekawa et al., 1991), and as CH₂Cl₂ solvate (Vicente et al., 1997; Kim et al., 2009). Here, we describe the structure of the title complex and its interaction with 1,4-dioxane as solvate.

The Pd complex crystallizes as 1,4-dioxane solvate and the solvent is determined as a half-molecule in the asymmetric unit; the symmetry operation 1 - x, 1 - y, 1 - z is necessary to generate the whole molecule. The title compound has similar values of bond distances and angles to the previously described CH₂Cl₂ solvate (Maekawa et al., 1991; Vicente et al., 1997; Kim et al., 2009). According to the Cremer & Pople puckering parameters (Cremer & Pople, 1975), the dioxane molecule has a chair conformation [Q=0.553 (8), θ=180.00 (1)°, φ =0°]. In the asymmetric unit, the O atom is bonded to H3—C3 and H9—C9 in a bifurcated fashion (Fig. 1). When the symmetry code (1 - x, 1 - y, 1 - z) is applied, a centrosymmetric structure of Pd complex–1,4-dioxane (2/1) is generated. In addition, the O atom is linked by O···H5—C5(bipy) (Table 1 and Fig. 2). As a result of these interactions, the bipyridine complexes are bonded by a weak π–π stacking interaction [Cg1(N1/C2–C6)···Cg2(N7/C8–C12) 3.817 (4) Å].

2. Experimental

To a solution of [Pd(MeCN)₂Cl₂] (0.13 g, 0.638 mmol) in acetone (10 ml), 2,2'-bipyridine (0.1 g, 0.64 mmol) was added under stirring. The resulting orange solution was allowed to react for 2 h under stirring at room temperature. After this time the solution was filtered and the solvent taken off under vacuum to produce a yellow solid of [(bipy)PdCl₂]. Crystals suitable for X-ray diffraction experiments were obtained from a dimethylformamide/dioxane solvent system at room temperature. ¹H NMR (DMSO-d₆): δ 7.83 (t, 1H, CH), 8.38 (t, 1H, CH), 8.60 (d, 1H, CH), 9.14 (d, 1H, CH); ¹³C{¹H}NMR (DMSO-D₆): δ 124.3 (s, CH), 127.8 (s, CH), 141.7 (s, CH). 150.1 (s, CH). 156.9 (s, C).