[1,2-Bis(diphenyl­phosphan­yl)ethane-κ2 P,P′]{2-[(4-nitro­benzoyl­meth­yl)diphenyl­phosphan­yl]phenyl-κ2 C,C′}palladium(II) trifluoro­methane­sulfonate–dichloro­methane–n-hexane (1/1/0.5)

Corrado Rizzoli; Kazem Karami; Farzaneh Borzooie

doi:10.1107/S1600536811008075

. 2011 Mar 9;67(Pt 4):m416–m417. doi: 10.1107/S1600536811008075

[1,2-Bis(diphenylphosphanyl)ethane-κ² P,P′]{2-[(4-nitrobenzoylmethyl)diphenylphosphanyl]phenyl-κ² C,C′}palladium(II) trifluoromethanesulfonate–dichloromethane–n-hexane (1/1/0.5)

Corrado Rizzoli ^a,^*, Kazem Karami ^b, Farzaneh Borzooie ^b

PMCID: PMC3099852 PMID: 21753947

Abstract

In the cation of the title compound, [Pd(C₂₆H₁₉NO₃P)(C₂₆H₂₄P₂)]CF₃O₃S·CH₂Cl₂·0.5C₆H₁₄, the Pd^II atom has a slightly tetrahedrally distorted square-planar coordination geometry. The PdC₃P and PdC₂P₂ five-membered metallacycles adopt envelope and twist conformations, respectively. In the crystal, intermolecular C—H⋯O hydrogen bonds link cations and anions into a three-dimensional network. The dichloromethane solvent molecule is disordered over three orientations with a site-occupancy ratio of 0.5/0.3/0.2. The n-hexane solvent molecule has a crystallographically imposed centre of symmetry.

Related literature

For the synthesis and applications as catalysts of cyclopalladated metal complexes, see: Rietling et al. (2002 ▶); Aguilar et al. (2008 ▶); Dupont et al. (2001 ▶); Chen et al. (2009 ▶). For ortho-palladated α-ketophosphorus ylides complexes reported by our group, see: Karami et al. (2010 ▶); Karami, Rizzoli & Salah (2011 ▶); Karami, Rizzoli & Borzooie (2011 ▶). For related structures, see: Falvello et al. (1998 ▶, 1999 ▶); Shao et al. (1982 ▶).

Experimental

Crystal data

[Pd(C₂₆H₁₉NO₃P)(C₂₆H₂₄P₂)]CF₃O₃S·CH₂Cl₂·0.5C₆H₁₄
M _r = 1206.27
Monoclinic,
a = 12.4063 (7) Å
b = 14.2445 (8) Å
c = 31.3633 (17) Å
β = 91.6675 (9)°
V = 5540.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.62 mm⁻¹
T = 294 K
0.19 × 0.16 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.872, T _max = 0.955
62924 measured reflections
10529 independent reflections
8106 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.076
S = 1.04
10529 reflections
691 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.38 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: APEX2; data reduction: SAINT (Bruker, 2008 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and SCHAKAL97 (Keller, 1997 ▶); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008075/zj2004sup1.cif

e-67-0m416-sup1.cif^{(34.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008075/zj2004Isup2.hkl

e-67-0m416-Isup2.hkl^{(514.9KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C19—H19⋯O1ⁱ	0.93	2.54	3.284 (3)	138
C30—H30⋯O6ⁱⁱ	0.93	2.55	3.372 (4)	148
C39—H39B⋯O6ⁱⁱⁱ	0.97	2.59	3.309 (4)	131

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

Financial support from the Universitá degli Studi di Parma is gratefully acknowledged.

supplementary crystallographic information

Comment

The synthesis and characterization of cyclopalladated metal complexes (Rietling et al., 2002) has attracted considerable attention due to their potential applications in organic synthesis and homogenous catalysis (Aguilar et al., 2008; Dupont et al., 2001; Chen et al., 2009). As a continuation of our ongoing project devoted to the development of new catalysts based on ortho-palladated α-ketophosphorus ylides complexes (Karami et al., 2010; Karami, Rizzoli & Salah, 2011; Karami, Rizzoli & Borzooie, 2011), we report herein the synthesis and crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) consists of one mononuclear complex cation, one trifluoromethanesulfonate anion, one disordered dichloromethane molecule and half an n-hexane lying on a centre of symmetry. In the cation (Fig. 2), the palladium(II) atom displays a slightly but not negligibly tetrahedrally distorted square planar coordination geometry, with atoms P2, P3, C1 and C9 displaced from the mean plane through the P₂C₂ core by -0.0061 (6), 0.0055 (6), -0.070 (2) and 0.069 (2) Å, respectively. The distortion from the regular square planar geometry is also indicated by the values of the cis and trans angles subtended at the metal, which range from 83.17 (8) to 100.49 (5)°, and from 175.31 (5) to 175.68 (5)°, respectively. The Pd–C bond lengths involving the aromatic and ylidic carbon atoms (Pd1–C9 = 2.0783 (19) Å; Pd–C1 = 2.1711 (19) Å) are in agreement with those observed in related cyclopalladated complexes (Falvello et al., 1998; Falvello et al., 1999; Karami et al., 2010; Karami, Rizzoli & Salah, 2011; Karami, Rizzoli & Borzooie, 2011). The P1–C1 bond length (1.768 (2) Å) is significantly longer than that observed in the related free ylide (1.711 Å) of formula PPh₃C(H)COPh (Shao et al., 1982). The Pd1···P1 separation is 3.0241 (9) Å. The PdC₃P five-membered metallacycle (Pd1/C9/C14/P1/C1) assumes an envelope conformation, with atom C1 displaced by 1.006 (2) Å from the mean planes of the remaining four atoms, whereas the PdC₂P₂ metallacycle (Pd1/P2/C39/C40/P3) adopts a twist conformation with the local twofold axis passing through the C39–C40 bond and the Pd atom. In the crystal structure (Fig. 3), cations and anions are linked into a three-dimensional network by intermolecular C—H···O hydrogen bonds (Table 1).

Experimental

The title compound was obtained according to the procedure recently reported elsewhere (Karami, Rizzoli & Borzooie, 2011). Crystals suitable for X-ray analysis were obtained by slow evaporation of a dichloromethane/n-hexane (1:1 v/v) solution at room temperature.