[1,2-Bis(diphenyl­phosphan­yl)ethane-κ2 P,P′]dichloridopalladium(II) dimethyl sulfoxide monosolvate

Ismail Warad; Abdullah S Aldwayyan; Fahad M Al-Jekhedab; M Iqbal Choudhary; Sammer Yousuf

doi:10.1107/S1600536812028310

. 2012 Jun 30;68(Pt 7):m984–m985. doi: 10.1107/S1600536812028310

[1,2-Bis(diphenylphosphanyl)ethane-κ² P,P′]dichloridopalladium(II) dimethyl sulfoxide monosolvate

Ismail Warad ^a, Abdullah S Aldwayyan ^b, Fahad M Al-Jekhedab ^c, M Iqbal Choudhary ^d,^a, Sammer Yousuf ^d,^*

PMCID: PMC3393233 PMID: 22807801

Abstract

In the title compound, [PdCl₂(C₂₆H₂₄P₂)]·C₂H₆OS, the Pd^II atom adopts a distorted cis-PdCl₂P₂ square-planar coordination geometry. The five-membered chelate ring adopts an envelope conformation with a methylene C atom in the flap position. The S and C atoms of the dimethyl sulfoxide (DMSO) solvent molecule are disordered over two sets of sites in a 0.8976 (18):0.1024 (18) ratio. The DMSO O atom accepts three C—H⋯O hydrogen bonds from an adjacent complex molecule.

Related literature

For the previous reports of crystal structures of this metal complex (unsolvated or with other solvents), see: Xu et al. (2008 ▶); Batsanov et al. (2001 ▶); Steffen & Palenik (1976 ▶); Singh et al. (1995 ▶).

Experimental

Crystal data

[PdCl₂(C₂₆H₂₄P₂)]·C₂H₆OS
M _r = 653.82
Triclinic,
a = 8.4091 (3) Å
b = 11.4745 (4) Å
c = 16.8098 (6) Å
α = 73.674 (1)°
β = 79.066 (1)°
γ = 68.634 (1)°
V = 1442.67 (9) Å³
Z = 2
Mo Kα radiation
μ = 1.03 mm⁻¹
T = 293 K
0.30 × 0.23 × 0.11 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.747, T _max = 0.895
19016 measured reflections
6610 independent reflections
5863 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.027
wR(F ²) = 0.069
S = 1.03
6610 reflections
326 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.32 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: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812028310/hb6864sup1.cif

e-68-0m984-sup1.cif^{(36.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028310/hb6864Isup2.hkl

e-68-0m984-Isup2.hkl^{(323.5KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Pd1—P2	2.2336 (5)
Pd1—P1	2.2355 (5)
Pd1—Cl1	2.3481 (6)
Pd1—Cl2	2.3613 (5)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1	0.93	2.49	3.348 (4)	153
C20—H20⋯O1	0.93	2.59	3.495 (4)	165
C26—H26A⋯O1	0.97	2.44	3.410 (3)	174

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Acknowledgments

The project was supported by King Saud University, Deanship of Scientific Research, College of Science Research Center. MIC and SY gratefully acknowledges the Pakistan Academy of Sciences for funding the project entitled ‘Study of molecular structures and drugability potential of new inhibitors of β-glucuronidase by single-crystal X-ray diffraction and NMR spectroscopic techniques’.

supplementary crystallographic information

Comment

Metal complexes containing chelating diphosphines as ligands have been employed in numerous catalytic processes. A major advantage of these ligands is variation in their potential catalytic reactivity by varying the molecular properties of the phosphine. The title compound was synthesized as a part of our ongoing research to study the properties of metal complexes with chelating ligands.

The crystal structure of title compound, [PdCl₂C₂₆H₂₄P₂)].C₆H₆SO, consists of a bidentate diphenyl phosphine ligand and two chloride atoms coordinated with Pd(II) to adapt a distorted square planner geometry, along with an independent molecule of dimethyl sulfoxide (DMSO) as solvent (Fig. 1). The five membered metallocycle (Pd1/P1/P2/C25—C26) adopts an envelop conformation [Q= 0.466 (19) Å and φ = 301.14 (17)°] with maximum deviation of 0.318 (2) Å for C26 atom from the least square plane. The Structural report of the compound is similar to many previously published reports with the difference that it has a DMSO solvate (Xu et al. 2008, Batsanov et al. 2001,Steffen & Palenik, 1976, Singh et al. 1995). The coordination environment around the Pd(II) ion is such that the two phosphorous atoms of the bidentate diphenyl phosphine ligand [Pd1–P1 = 2.2355 (5) Å, Pd1–P2 = 2.2336 (5) Å] and two chloride atoms [Pd1–Cl1= 2.3481 (6) Å, Pd1–Cl2= 2.3613 (5) Å] are assembled at four corners of square to adapt square pyramidal arrangement. The S1, C28 and C29 atoms of DMSO molecule are disordered at two positions,with relative occupancies of 0.89 (18):0.10 (18) for the isotropically refined major (S1/C27/C28) and minor (S1'/C27'/C28') components, respectively. All bond lengths are in agreement with the previously reported crystal structures (Xu et al. 2008, Batsanov et al. 2001, Steffen & Palenik, 1976, Singh et al. 1995). The oxygen atom of DMSO playing an important role in the crystal structure by forming C2—H2···O1, C20—H20···O1 and C26—H26A···O1 hydrogen bonds (Table 2, Fig. 2).

The compound was evaluated for its b-glucoronidase inhibiton activity against D-saccharic acid as standard (IC₅₀ 45.75 ± 2.16 mM) and found as weak inhibitor (IC₅₀ 197.3 ± 12.2 mM)

Experimental

Equimolar amounts of dichlorobis(acetonitrile) palladium(II) (0.10 g, 0.26 mmol) was dissolved in 10 ml dry dichloromethane and mixed with equivalent amount of 1,2-ethanediylbis(diphenylphosphine) (0.11 g, 0.27 mmol). The resultant mixture was stirred under inert atmosphere (Ar) for about one hour. The solution was concentrated under reduced pressure to 1 ml volume. The product was precipitated by the addition of 30 ml of hexane. Then filtered off, washed with 40 ml of diethyl ether and dried under vacuum to obtained 0.12 g of title compound I (yield 78%). 20 mg of the product was dissolved in 5 ml of dry DMSO for crystallization. After one week, light orange color crystals were obtained which were found to be suitable for X-ray diffraction data collection. All chemicals were purchased from Acros (Belgium).