[μ-Bis(diphenyl­arsino)methane-1:2κ2 As:As’]nona­carbonyl-1κ3 C,2κ3 C,3κ3 C-(triphenyl phosphite-3κP)-triangulo-triruthenium(0)

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

doi:10.1107/S1600536810001200

. 2010 Jan 30;66(Pt 2):m223–m224. doi: 10.1107/S1600536810001200

[μ-Bis(diphenylarsino)methane-1:2κ² As:As’]nonacarbonyl-1κ³ C,2κ³ C,3κ³ C-(triphenyl phosphite-3κP)-triangulo-triruthenium(0)

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

PMCID: PMC2979706 PMID: 21579683

Abstract

The asymmetric unit of the title triangulo-triruthenium compound, [Ru₃(C₂₅H₂₂As₂)(C₁₈H₁₅O₃P)(CO)₉], contains two crystallographically independent but similar molecules. The bis(diphenylarsino)methane ligand bridges an Ru—Ru bond and the monodentate phosphite ligand bonds to the third Ru atom. Both the phosphite and arsine ligands are equatorial with respect to the Ru₃ triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. One of the triphenylphosphite benzene rings in one of the molecules is disordered over two positions with refined site occupancies of 0.60 (3) and 0.40 (3). In the crystal packing, the molecules are stacked along a axis. Intramolecular C—H⋯O hydrogen bonds stabilize the molecular structure and weak intermolecular C—H⋯π interactions further stabilize the crystal structure. The crystal studied was a non-merohedral twin, the refined ratio of the twin components being 0.618 (1):0.382 (1).

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 μ-bis(diphenylarsino)methanedecacarbonyltriruthenium(0), see: Bruce et al. (1983 ▶). For stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Ru₃(C₂₅H₂₂As₂)(C₁₈H₁₅O₃P)(CO)₉]
M _r = 1337.84
Monoclinic,
a = 15.6537 (3) Å
b = 21.3662 (4) Å
c = 30.1698 (6) Å
β = 90.125 (1)°
V = 10090.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 2.28 mm⁻¹
T = 100 K
0.25 × 0.23 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.604, T _max = 0.918
235438 measured reflections
29385 independent reflections
22171 reflections with I > 2σ(I)
R _int = 0.080

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.132
S = 1.07
29385 reflections
1275 parameters
174 restraints
H-atom parameters constrained
Δρ_max = 2.75 e Å⁻³
Δρ_min = −2.02 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/S1600536810001200/tk2607sup1.cif

e-66-0m223-sup1.cif^{(74KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810001200/tk2607Isup2.hkl

e-66-0m223-Isup2.hkl^{(1.4MB, hkl)}

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

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

Cg1, Cg2, Cg3, Cg4, Cg5, Cg6 and Cg7 are the centroids of the C1B–C6B, C1A–C6A, C14A–C19A, C14A–C19A, C7A–C12A, C20B–C25B and C20A–C25A benzene rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C31A—H31A⋯O12A	0.93	2.42	3.014 (13)	121
C39A—H39A⋯O11A	0.93	2.38	2.959 (11)	120
C43B—H43B⋯O2B	0.93	2.53	3.42 (2)	158
C11A—H11A⋯Cg1ⁱ	0.93	2.95	3.742 (12)	144
C11B—H11B⋯Cg2ⁱⁱ	0.93	2.85	3.664 (10)	147
C16A—H16A⋯Cg1ⁱⁱⁱ	0.93	2.82	3.668 (10)	151
C16B—H16B⋯Cg2	0.93	2.82	3.627 (10)	146
C24A—H24A⋯Cg3^iv	0.93	2.96	3.719 (10)	140
C24B—H24B⋯Cg4^v	0.93	2.91	3.679 (10)	141
C36B—H36B⋯Cg5ⁱⁱ	0.93	2.85	3.756 (12)	166
C40A—H40A⋯Cg6^vi	0.93	2.82	3.660 (10)	150
C40B—H40B⋯Cg7^vii	0.93	2.71	3.55 (2)	150
C40C—H40C⋯Cg7^vii	0.93	2.70	3.56 (3)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

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, Liddell et al., 1988a, b; Bruce et al., 1985). 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(C₁₈H₁₅O₃P)(C₂₅H₂₂As₂)(CO)₉.

The asymmetric unit consists of two crystallographically independent molecules of the triangulo-triruthenium complex, A and B (Fig. 1). The bond lengths and angles of title compound are comparable to those found in a closely related structure (Shawkataly et al., 2009). The bis(diphenylarsino)methane ligand bridges the Ru1—Ru2 bond and the monodentate phosphine ligand bonds to the Ru3 atom. Both the phosphine 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 triphenylphosphite benzene rings make dihedral angles (C26–C31/C32–C37, C26–C31/C38–C43 and C32–C37/C38–C43) of 66.9 (5), 55.6 (5) and 62.0 (5)° with each other in molecule A whereas these angles are 85.5 (5), 71.4 (9) and 85.8 (9)° (major component), 85.5 (5), 71.2 (11) and 85.1 (11)° (minor component) in molecule B. The dihedral angles between the two benzene rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 84.7 (4) and 84.0 (4)° for the two diphenylarsino groups in molecule A whereas these angles are 85.0 (4) and 86.3 (4)° in molecule B. In the crystal structure, the molecules are stacked along a axis (Fig. 2). Intramolecular C31A—H31A···O11A, C39A—H39A···O12A and C43B—H43B···O2B hydrogen bonds stabilize the molecular structure and 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, and all solvents were dried over sodium and distilled from sodium benzophenone ketyl under nitrogen. Triphenylphosphite (BDH) was used as received and µ-bis(diphenylarsino)methanedecacarbonyltriruthenium(0) was prepared by a reported procedure (Bruce et al., 1983). The title compound was obtained by refluxing equimolar quantities of Ru₃(CO)₁₀(µ-Ph₂AsCH₂AsPh₂) (105.5 mg, 0.1 mmol) and triphenylphosphite (31.0 mg, 0.1 mmol) in hexane under nitrogen atmosphere. Crystals were grown by slow solvent / solvent diffusion of CH₃OH into CH₂Cl₂.