[μ-Bis(diphenyl­arsan­yl)methane-1:2κ2 As:As’]nona­carbonyl-1κ3 C,2κ3 C,3κ3 C-[tris­(biphenyl-4-yl)arsane-3κAs]-triangulo-triruthenium(0)

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

doi:10.1107/S1600536811000237

. 2011 Jan 15;67(Pt 2):m214–m215. doi: 10.1107/S1600536811000237

[μ-Bis(diphenylarsanyl)methane-1:2κ² As:As’]nonacarbonyl-1κ³ C,2κ³ C,3κ³ C-[tris(biphenyl-4-yl)arsane-3κAs]-triangulo-triruthenium(0)

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

PMCID: PMC3051569 PMID: 21522877

Abstract

In the title triangulo-triruthenium compound, [Ru₃(C₂₅H₂₂As₂)(C₃₆H₂₇As)(CO)₉], the bis(diphenylarsanyl)methane ligand bridges an Ru—Ru bond and the monodentate arsine ligand bonds to the third Ru atom. Both arsine ligands are equatorial with respect to the Ru₃ triangle. In addition, each Ru atom carries one equatorial and two axial terminal carbonyl ligands. The phenyl rings of biphenyl are twisted from each other by dihedral angles of 50.5 (2), 44.5 (2) and 27.8 (2)°. The arsine-substituted phenyl rings make dihedral angles of 61.56 (18), 89.36 (18) and 83.27 (18)° with each other. The dihedral angles between the two benzene rings are 87.5 (2) and 81.95 (19)° for the two diphenylarsanyl groups. In the crystal, molecules are linked into dimers by intermolecular C—H⋯O hydrogen bonds. Weak intermolecular C—H⋯π and π–π [centroid–centroid distance = 3.601 (3) Å] interactions 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 ▶, 2010 ▶, 2011 ▶). For the synthesis of Ru₃(CO)₁₀(μ-Ph₂AsCH₂AsPh₂), see: Bruce et al. (1983 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Ru₃(C₂₅H₂₂As₂)(C₃₆H₂₇As)(CO)₉]
M _r = 1562.06
Triclinic,
a = 10.906 (4) Å
b = 12.706 (4) Å
c = 22.467 (8) Å
α = 81.249 (7)°
β = 82.529 (7)°
γ = 79.301 (7)°
V = 3006.8 (18) Å³
Z = 2
Mo Kα radiation
μ = 2.44 mm⁻¹
T = 100 K
0.47 × 0.28 × 0.04 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.396, T _max = 0.900
60960 measured reflections
17294 independent reflections
13951 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.125
S = 1.11
17294 reflections
766 parameters
H-atom parameters constrained
Δρ_max = 1.42 e Å⁻³
Δρ_min = −0.69 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/S1600536811000237/ng5094sup1.cif

e-67-0m214-sup1.cif^{(47.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000237/ng5094Isup2.hkl

e-67-0m214-Isup2.hkl^{(845.2KB, hkl)}

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

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

Cg1 is the centroid of the C26–C31 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C46—H46A⋯O9ⁱ	0.93	2.56	3.251 (6)	131
C24—H24A⋯Cg1ⁱⁱ	0.93	2.95	3.625 (5)	130

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

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 Visiting Researcher position. SSS thanks USM for the G A position. HKF and CSY thank USM for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

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, 2010). Herein we report the synthesis and structure of the title compound.

The bis(diphenylarsanyl)methane ligand bridges the Ru1–Ru2 bond and the monodentate arsine ligand bonds to the Ru3 atom. Both arsine ligands are equatorial with respect to the Ru₃ triangle. Additionally, each Ru atom carries one equatorial and two axial terminal carbonyl ligands (Fig 1). The phenyl rings of biphenyl (C26–C31/C32–C37, C38–C43/C44–C49 and C50–C55/C56–C61) make dihedral angles of 50.5 (2), 44.5 (2) and 27.8 (2)° from each other respectively. These angles are more twisted from each other compare to the reported monodentate arsine ligand (Shawkataly et al., 2011). The arsine-substituted phenyl rings make dihedral angles (C26–C31/C38–C43, C26–C31/C50–C55 and C38–C43/C50–C55) of 61.56 (18), 89.36 (18) and 83.27 (18)° with each other respectively. The dihedral angles between the two benzene rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 87.5 (2) and 81.95 (19)° for the two diphenylarsanyl groups respectively.

In the crystal packing, the molecules are linked into dimers by intermolecular C46—H46A···O9 hydrogen bonds (Fig. 2, Table 1). Weak intermolecular C—H···π (Table 1) and Cg2···Cg2 interactions stabilize the crystal structure. Cg2···Cg2ⁱⁱⁱ = 3.601 (3) Å; Cg2 is centroid of C14–C19; (iii) 2 - x,2 - y,-z.

Experimental

All manipulations were performed under a dry oxygen-free nitrogen atmosphere using standard Schlenk techniques. All solvents were dried over sodium and distilled from sodium benzophenone ketyl under dry oxygen free nitrogen. Tri([1,1'-biphenyl]-4-yl)arsine is prepared by the reaction of AsCl₃ with biphenyl magnesiumbromide in THF and Ru₃(CO)₁₀(µ-Ph₂AsCH₂AsPh₂) (Bruce et al., 1983) was prepared by reported procedure. The title compound was obtained by refluxing equimolar quantities of Ru₃(CO)₁₀(µ-Ph₂AsCH₂AsPh₂) and tri([1,1'-biphenyl]-4-yl)arsine in hexane under nitrogen atmosphere. Crystals suitable for X-ray diffraction were grown by slow solvent / solvent diffusion of CH₃OH into CH₂Cl₂.