Bis{[μ-bis­(diphenyl­phosphino)methane-1:2κ2 P:P′]nona­carbonyl-1κ3 C,2κ3 C,3κ3 C-[tris­(4-methoxy­phen­yl)arsine-3κAs]-triangulo-triruthenium(0)} dichloro­methane solvate

Omar bin Shawkataly; Imthyaz Ahmed Khan; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536809052088

. 2009 Dec 9;66(Pt 1):m30–m31. doi: 10.1107/S1600536809052088

Bis{[μ-bis(diphenylphosphino)methane-1:2κ² P:P′]nonacarbonyl-1κ³ C,2κ³ C,3κ³ C-[tris(4-methoxyphenyl)arsine-3κAs]-triangulo-triruthenium(0)} dichloromethane solvate

Omar bin Shawkataly ^a,^*,^‡, Imthyaz Ahmed Khan ^a, Chin Sing Yeap ^b,^§, Hoong-Kun Fun ^b,^¶

PMCID: PMC2980253 PMID: 21579930

Abstract

The asymmetric unit of the title triangulo-triruthenium compound, 2[Ru₃(C₂₁H₂₁AsO₃)(C₂₅H₂₂P₂)(CO)₉]·CH₂Cl₂, contains one triangulo-triruthenium complex molecule and one half-molecule of the dichloromethane solvent. The dichloromethane solvent lies across a crystallographic inversion center leading to the molecule being disordered over two positions of equal occupancy. The bis(diphenylphosphino)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru₃ triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsine-substituted benzene rings make dihedral angles of 82.00 (6), 76.67 (7) and 66.09 (6)° with each other. The dihedral angles between the two benzene rings are 80.12 (8) and 78.34 (7)° for the two diphenylphosphino groups. In the crystal packing, the molecules are linked together into chains down the b axis via intermolecular C—H⋯O hydrogen bonds. An intermolecular C—H⋯O hydrogen bond and weak intermolecular C—H⋯π interactions further stabilize the crystal structure.

Related literature

For general background to triangulo-triruthenium derivatives, see: Bruce et al. (1985 ▶, 1988a ▶,b ▶). For related structures, see: Shawkataly et al. (1998 ▶, 2004 ▶, 2009 ▶). For the synthesis of tris(4-methoxyphenyl)arsine, see: Blicke & Cataline (1938 ▶) and for that of μ-bis(diphenylphosphino)methanedecacarbonyltriruthenium(0), see: Bruce et al. (1983 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

2[Ru₃(C₂₁H₂₁AsO₃)(C₂₅H₂₂P₂)(CO)₉]·CH₂Cl₂
M _r = 2756.85
Triclinic,
a = 10.7428 (1) Å
b = 12.6731 (1) Å
c = 20.6529 (2) Å
α = 95.523 (1)°
β = 101.315 (1)°
γ = 103.929 (1)°
V = 2645.47 (4) Å³
Z = 1
Mo Kα radiation
μ = 1.64 mm⁻¹
T = 100 K
0.30 × 0.23 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.637, T _max = 0.797
123575 measured reflections
23203 independent reflections
20247 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.023
wR(F ²) = 0.055
S = 1.02
23203 reflections
679 parameters
H-atom parameters constrained
Δρ_max = 1.72 e Å⁻³
Δρ_min = −1.34 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809052088/sj2701sup1.cif

e-66-00m30-sup1.cif^{(44.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809052088/sj2701Isup2.hkl

e-66-00m30-Isup2.hkl^{(1.1MB, 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
C53—H53C⋯O2ⁱ	0.96	2.60	3.346 (2)	135
C56—H56A⋯O7	0.96	2.60	3.116 (3)	114
C22—H22A⋯Cg1ⁱⁱ	0.93	2.91	3.5901 (16)	131
C53—H53B⋯Cg2ⁱⁱⁱ	0.96	2.85	3.6951 (17)	147

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of theC32–C37 and C26–C31 benzene rings, respectively.

Acknowledgments

The authors would like to thank the Malaysian Government and Universiti Sains Malaysia (USM) for the Research grant 1001/PJJAUH/811115. IAK is grateful to USM for a Postdoctoral Fellowship and to Gokhale Centenary College, Ankola, Karnataka, India, for postdoctoral study leave. HKF thanks USM for the Research University Golden Goose grant 1001/PFIZIK/811012. CSY thanks USM for the award of a USM Fellowship.

supplementary crystallographic information

Comment

Triangulo-triruthenium clusters are known for their interesting structural variations and related catalytic activity. A large number of substituted derivatives, Ru₃(CO)_12-nL_n (L = group 15 ligand) have been reported (Bruce et al., 1985, 1988a,b). As part of our study of the substitution of transition metal-carbonyl clusters with mixed-ligand complexes, we have published several structures of triangulo-triruthenium-carbonyl clusters containing mixed P/As and P/Sb ligands (Shawkataly et al., 1998, 2004, 2009). Herein we report the synthesis and structure of the title compound.

The asymmetric unit consists of one molecule of triangulo-triruthenium complex and half a molecule of dichloromethane solvent (Fig. 1). The dichloromethane solvent lies across a crystallographic inversion center (symmetry code: 2 - x, 1 - y, -z) leading to disorder of this solvent molecule over two positions. The bond lengths and angles of title compound are comparable to those found in related structures (Shawkataly et al., 2009). The bis(diphenylphosphino)methane ligand bridges the Ru1—Ru2 bond and the monodentate arsine ligand bonds to the Ru3 atom. Both the arsine and phosphine ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three arsine-substituted benzene rings make dihedral angles (C26–C31/C32–C37, C26–C31/C38–C43 and C32–C37/C38–C43) of 82.00 (6), 76.67 (7) and 66.09 (6)° with each other respectively. The dihedral angles between the two benzene rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 80.12 (8) and 78.34 (7)° for the two diphenylphosphino groups respectively.

In the crystal packing (Fig. 2), the molecules are linked together into chains via intermolecular C53—H53C···O2 contacts along the b axis. An intermolecular C56—H56A···O7 hydrogen bond and weak intermolecular C—H···π interactions further stabilize the crystal structure (Table 1).

Experimental

The reactions were conducted under an atmosphere of high purity nitrogen using standard Schlenk techniques and hexane-dried over sodium metal. Tris(4-methoxyphenyl)arsine (Blicke et al., 1938) and µ-bis(diphenylphosphino)methanedecacarbonyltriruthenium(0) (Bruce et al., 1983) were prepared by reported procedures. The title compound was obtained by refluxing equimolar quantities of Ru₃(CO)₁₀(µ-Ph₂PCH₂PPh₂) (102.4 mg, 0.1 mmol) and tris(4-methoxyphenyl)arsine (39.63 mg, 0.1 mmol) in hexane under a nitrogen atmosphere. Crystals suitable for X-ray diffraction were grown by slow solvent / solvent diffusion of CH₃OH into CH₂Cl₂.