Dichlorido{N-[2-(diphenyl­phosphan­yl)benzyl­idene]isopropyl­amine-κ2 N,P}palladium(II) dimethyl sulfoxide monosolvate

Haleden Chiririwa; Reinout Meijboom; Bernard Omondi

doi:10.1107/S1600536811013936

. 2011 Apr 16;67(Pt 5):m608–m609. doi: 10.1107/S1600536811013936

Dichlorido{N-[2-(diphenylphosphanyl)benzylidene]isopropylamine-κ² N,P}palladium(II) dimethyl sulfoxide monosolvate

Haleden Chiririwa ^a,^*, Reinout Meijboom ^b, Bernard Omondi ^b

PMCID: PMC3089087 PMID: 21754326

Abstract

In the title Pd^II complex, [PdCl₂(C₂₂H₂₂NP)]·(CH₃)₂SO, the Pd^II atom is coordinated in an NPCl₂ coordination sphere by the N(imino) and P(phosphane) atoms of the ligand and by two Cl⁻ ions in a slightly distorted square-planar geometry [r.m.s. deviation = 0.081 (3) Å, plane defined by the four atoms around the Pd atom]. The dimethyl sulfoxide solvent molecules form centrosymmetric dimers due to an intermolecular C—H⋯O interaction. The crystal structure is further stabilized through two intermolecular C—H⋯π interactions.

Related literature

For structures with related ligands, see: Ghilardi et al. (1992 ▶); Sanchez et al. (1998 ▶, 2001 ▶).

Experimental

Crystal data

[PdCl₂(C₂₂H₂₂NP)]·C₂H₆OS
M _r = 586.8
Triclinic,
a = 8.9935 (2) Å
b = 10.0413 (2) Å
c = 13.9439 (3) Å
α = 91.189 (1)°
β = 97.957 (1)°
γ = 94.869 (1)°
V = 1241.93 (5) Å³
Z = 2
Mo Kα radiation
μ = 1.13 mm⁻¹
T = 173 K
0.20 × 0.10 × 0.05 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (XPREP; Sheldrick, 2008 ▶) T _min = 0.806, T _max = 0.946
45019 measured reflections
6342 independent reflections
5437 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.069
S = 1.04
6342 reflections
284 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.59 e Å⁻³

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶) and ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013936/go2010sup1.cif

e-67-0m608-sup1.cif^{(23.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013936/go2010Isup2.hkl

e-67-0m608-Isup2.hkl^{(304.1KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pd1—N24	2.0725 (17)
Pd1—P4	2.2188 (5)
Pd1—Cl3	2.2826 (5)
Pd1—Cl2	2.3838 (5)

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

Cg3 and Cg4 are the centroids of the C11–C16 and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C31—H31A⋯O29ⁱ	0.98	2.50	3.481 (4)	174
C10—H10⋯Cg3ⁱⁱ	0.95	2.84	3.643 (2)	146
C8—H8⋯Cg4ⁱⁱⁱ	0.95	2.74	3.577 (3)	147

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

Acknowledgments

We gratefully acknowledge Mintek and Project AuTEK for funding this project.

supplementary crystallographic information

Comment

In recent years, palladium complexes with iminophosphane ligands of the N-[(2-diphenylphosphanyl)benzylidene]amine type have been used as catalysts (or catalyst precursors) in a variety organic reactions. To the best of our knowledge, only a few structures have been determined so far, concerning the free ligand (2-diphenylphosphanyl-benzylidene)-isopropyl-amine, where the potentially bidentate ligand is chelated to the metal through the phosphorus and imino nitrogen atoms (Fig. 1). The title compound (I) has been synthesized earlier but there have been no reports of the crystal structure: the Pd^II center adopts a slightly distorted square planar geometry in with an r.m.s. deviation of 0.081 (3) Å from the planar geometry. Selected bond lengths are given in table 1.

In the structure of (I) the (CH₃)₂SO molecules are connected through a weak C—H···O intermolecular interaction forming centrosymmetric dimers (Fig. 2). In addition, the crystal lattice is further stabilized through two C—H···π intermolecular interactions (Fig 3). C10—H10···π (Cg of C11 to C16 atoms ring) joins two of the complex molecules into centrosymmetric dimers. Those combined with the C8—H8···π (Cg of C17 to C22 atoms ring) interaction, make additional rings composed of four complex molecules for further stabilization of the crystal lattice.

Experimental

To a dry CH₂Cl₂ (10 ml) solution of the precursor [Pd(COD)Cl₂] (0.095 g, 0.3 mmol) was added isopropylamine (0.018 g, 0.3 mmol) in CH₂Cl₂ (10 ml) solution, and the reaction was stirred at room temperature for 1 hr. The yellow solution was concentrated under reduced pressure to half volume and the addition of ca 10 ml hexane caused precipitation of the complex, which was filtered off, washed with Et₂O and dried under vacuum for 4 hrs. Yellow crystals used in the X-ray diffraction studies were grown by slow evaporation of a solution of the compound in a CH₂Cl_2/(CH₃)₂SO (1:1) solution at room temperature.