[μ-Bis(diphenyl­arsino)methane-1:2κ2 As:As′]nona­carbonyl-1κ3 C,2κ3 C,3κ3 C-[triphenyl­stibine-3κSb]-triangulo-triruthenium(0)

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

doi:10.1107/S1600536809049927

. 2009 Dec 24;66(Pt 1):m94–m95. doi: 10.1107/S1600536809049927

[μ-Bis(diphenylarsino)methane-1:2κ² As:As′]nonacarbonyl-1κ³ C,2κ³ C,3κ³ C-[triphenylstibine-3κSb]-triangulo-triruthenium(0)

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

PMCID: PMC2980229 PMID: 21579984

Abstract

In the title triangulo-triruthenium compound, [Ru₃(C₂₅H₂₂As₂)(C₁₈H₁₅Sb)(CO)₉], the bis(diphenylarsino)methane ligand bridges an Ru—Ru bond and the monodentate stibine ligand bonds to the third Ru atom. Both the stibine and arsine ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three stibine-substituted phenyl rings make dihedral angles of 84.3 (3), 80.4 (3) and 70.5 (3)° with each other. The dihedral angles between the two phenyl rings are 85.9 (3) and 75.2 (3)° for the two diphenylarsine groups. In the crystal packing, molecules are linked into chains down the c axis via intermolecular C—H⋯O hydrogen bonds. 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 ▶); Shawkataly et al. (1998 ▶, 2004 ▶, 2009 ▶). For related structures, see: Shawkataly et al. (2009 ▶). For the synthesis of μ-bis(diphenylarsino)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

[Ru₃(C₂₅H₂₂As₂)(C₁₈H₁₅Sb)(CO)₉]
M _r = 1380.62
Monoclinic,
a = 42.3464 (6) Å
b = 11.6246 (2) Å
c = 20.1185 (3) Å
β = 91.823 (1)°
V = 9898.5 (3) Å³
Z = 8
Mo Kα radiation
μ = 2.82 mm⁻¹
T = 100 K
0.36 × 0.15 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.428, T _max = 0.796
55374 measured reflections
11349 independent reflections
8669 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.096
S = 1.08
11349 reflections
605 parameters
H-atom parameters constrained
Δρ_max = 1.45 e Å⁻³
Δρ_min = −1.24 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/S1600536809049927/sj2682sup1.cif

e-66-00m94-sup1.cif^{(39.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049927/sj2682Isup2.hkl

e-66-00m94-Isup2.hkl^{(555KB, 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
C13—H13B⋯O8ⁱ	0.97	2.59	3.290 (7)	129
C23—H23A⋯Cg1ⁱⁱ	0.93	2.88	3.686 (6)	146
C34—H34A⋯Cg2ⁱⁱⁱ	0.93	2.72	3.564 (6)	151

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of the C14–C19 and C26–C31phenyl 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 on 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 Ru₃(C₁₈H₁₅Sb)(C₂₅H₂₂As₂)(CO)₉.

The bond lengths and angles of title compound (Fig. 1) are comparable to those found in a related structure (Shawkataly et al., 2009). The bis(diphenylarsino)methane ligand bridges the Ru1—Ru2 bond and the monodentate stibine ligand bonds to the Ru3 atom. Both the stibine and arsine ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The three stibine substituted phenyl rings make dihedral angles (C26–C31/C32–C37, C26–C31/C38–C43 and C32–C37/C38–C43) of 84.3 (3), 80.4 (3) and 70.5 (3)° with each other respectively. The dihedral angles between the two phenyl rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 85.9 (3) and 75.2 (3)° for the two diphenylarsino groups respectively.

In the crystal packing (Fig. 2), the molecules are linked together into chains via intermolecular C13—H13B···O8 along c axis. Weak intermolecular C—H···π interactions further stabilize the crystal structure (Table 1).

Experimental

All manipulations were performed under a dry oxygen-free dinitrogen atmosphere using standard Schlenk techniques, all solvents were dried over sodium and distilled from sodium benzophenone ketyl under nitrogen. Triphenylstibine (Fluka) used as received and µ-bis(diphenylarsino)methanedecacarbonyltriruthenium(0) (Bruce et al., 1983) was prepared by reported procedure. The title compound was obtained by refluxing equimolar quantities of Ru₃(CO)₁₀(µ-Ph₂AsCH₂AsPh₂) (105.5 mg, 0.1 mmol) and triphenylstibine (35.3 mg, 0.1 mmol) in hexane under nitrogen atmosphere. Crystals suitable for X-ray diffraction were grown by slow solvent / solvent diffusion of CH₃OH into CH₂Cl₂.