[μ-Bis(diphenyl­arsanyl)methane-1:2κ2 As:As′]nona­carbonyl-1κ3C,2κ3C,3κ3C-(triisoprop­yl phos­phite-3κP)-triangulo-triruthenium(0)

Omar bin Shawkataly; Mohd Gulfam Alam; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536811012050

. 2011 Apr 7;67(Pt 5):m545–m546. doi: 10.1107/S1600536811012050

[μ-Bis(diphenylarsanyl)methane-1:2κ² As:As′]nonacarbonyl-1κ³C,2κ³C,3κ³C-(triisopropyl phosphite-3κP)-triangulo-triruthenium(0)

Omar bin Shawkataly ^a,^*,^‡, Mohd Gulfam Alam ^a,^§, Chin Sing Yeap ^b,^¶, Hoong-Kun Fun ^b,^‡‡

PMCID: PMC3089132 PMID: 21754283

Abstract

The asymmetric unit of the title triangulo-triruthenium compound, Ru₃(CO)₉(μ-Ph₂AsCH₂AsPh₂)(P[OCH(CH₃)₂]₃) or [Ru₃(C₂₅H₂₂As₂)(C₉H₂₁O₃P)(CO)₉], contains two molecules of the triangulo-triruthenium complex. The bis(diphenylarsanyl)methane ligand bridges an Ru—Ru bond and the monodentate phosphite ligand binds to the third Ru atom. Both the arsine and phosphite ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The dihedral angles between the pairs of benzene rings bound to individual As atoms are 85.67 (8) and 75.91 (8) in the first independent molecule and 74.64 (8) and 70.76 (9) in the second. In the crystal, molecules are linked into a three-dimensional framework by intermolecular C—H⋯O hydrogen bonds.

Related literature

For related structures, see: Bruce et al. (1983 ▶, 1988 ▶); Churchill et al. (1977 ▶); Shawkataly et al. (1998 ▶). For the synthesis, see: Shawkataly et al. (2011 ▶); Bruce et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Ru₃(C₂₅H₂₂As₂)(C₉H₂₁O₃P)(CO)₉]
M _r = 1235.79
Triclinic,
a = 12.3481 (3) Å
b = 18.1697 (4) Å
c = 21.5295 (5) Å
α = 93.494 (1)°
β = 103.230 (1)°
γ = 90.383 (1)°
V = 4692.38 (19) Å³
Z = 4
Mo Kα radiation
μ = 2.45 mm⁻¹
T = 100 K
0.35 × 0.23 × 0.19 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.483, T _max = 0.659
161249 measured reflections
40931 independent reflections
35153 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.055
S = 1.01
40931 reflections
1093 parameters
H-atom parameters constrained
Δρ_max = 1.57 e Å⁻³
Δρ_min = −1.26 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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/S1600536811012050/sj5121sup1.cif

e-67-0m545-sup1.cif^{(72.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012050/sj5121Isup2.hkl

e-67-0m545-Isup2.hkl^{(2MB, 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
C10B—H10B⋯O6Aⁱ	0.93	2.59	3.293 (2)	132
C17B—H17B⋯O2Bⁱⁱ	0.93	2.57	3.477 (2)	165
C33A—H33B⋯O2Aⁱⁱⁱ	0.96	2.56	3.492 (2)	164

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

Acknowledgments

We gratefully acknowledge funding from the Malaysian Government and Universiti Sains Malaysia (USM) under the University Research Grant 1001/PJJAUH/811115. MGA thanks USM for a dost-doctoral fellowship and HKF thanks the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Syntheses and crystal structures of substituted triangulo-triruthenium clusters have been of interest to researchers due to structural variations and catalytic activities. A large number of substituted derivatives, Ru₃(CO)_12-nL_n (L = group 15 ligand) have been reported (Bruce et al., 1988). As part of our ongoing studies (Shawkataly et al., 2011), we report here a mixed-ligand metal-carbonyl cluster complex, Ru₃(CO)₉(µ-Ph₂AsCH₂AsPh₂)(P[OCH(CH₃)₂]₃).

The asymmetric unit consists of two crystallographically independent molecules (Fig. 1) of the triangulo-triruthenium complex, A and B. Fig. 2 shows the atom numbering scheme for molecule A. Atoms of molecule B were labelled similarly. The bond lengths and angles of the title compound are comparable to those found in its related structure (Shawkataly et al., 1998). The bis(diphenylarsino)methane ligand bridges the Ru1 – Ru2 bond and the monodentate phosphite ligand bonds to the Ru3 atom. Both the phosphite 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 dihedral angles between the two benzene rings (C1-C6/C7-C12 & C14-C19/C20-C25) are 85.67 (8), 75.91 (8) and 74.64 (8), 70.76 (9) for the two diphenylarsanyl groups of molecule A and B, respectively.

In the title compound, one of the Ru – Ru bonds is noticeably longer compared to the other two Ru – Ru bonds. The unevenness in the lengths of Ru – Ru bonds in comparison with those of the Ru₃(CO)₁₂ structure (Churchill et al., 1977), can be attributed to the steric effect induced by the bulky substituent. In the crystal, molecules are linked into a three-dimensional framework by intermolecular C—H···O weak intearctions. (Fig. 3).

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 (Bruce et al., 1987). Isopropyl phosphite was used as received and bis(diphenylarsino)methane (Bruce et al., 1983) was prepared by the reported procedure.

Equimolar quantities of Ru₃(CO)₁₀(µ-Ph₂AsCH₂AsPh) and isopropyl phosphite were refluxed in THF under nitrogen for 20 minutes. The reaction mixture turned intense red. The solvent was removed under vacuum. The reaction mixture was separated by TLC (dichloromethane:hexane, 1:3). Two bands appeared. The major band (red) R_f= 0.61 was separated and characterized. The compound was crystallised from CH₂Cl₂- CH₃OH, 1:3 yield = 55.2 %, m.p. 189°C. IR(cyclohexane): v (CO) 2127s, 2059 vs, 2042 s, 2017 s, 1988 s cm^-1.