[μ-1,6-Bis(diphenyphosphan­yl)hexane-1:2κ2 P:P′]deca­carbonyl-1κ3 C,2κ3 C,3κ4 C-triangulo-triruthenium(0)

Omar bin Shawkataly; Siti Syaida Sirat; Ching Kheng Quah; Hoong-Kun Fun

doi:10.1107/S1600536812014614

. 2012 Apr 18;68(Pt 5):m629–m630. doi: 10.1107/S1600536812014614

[μ-1,6-Bis(diphenyphosphanyl)hexane-1:2κ² P:P′]decacarbonyl-1κ³ C,2κ³ C,3κ⁴ C-triangulo-triruthenium(0)

Omar bin Shawkataly ^a,^*,^‡, Siti Syaida Sirat ^a,^§, Ching Kheng Quah ^b,^¶, Hoong-Kun Fun ^b,^‡‡

PMCID: PMC3344360 PMID: 22590126

Abstract

The title triangulo-triruthenium(0) compound, [Ru₃(C₃₀H₃₂P₂)(CO)₁₀], contains a triangle of singly bonded Ru atoms. The phosphane-bridged Ru—Ru distance [2.9531 (2) Å] is significantly longer than the non-bridged Ru—Ru distances [2.8842 (2) and 2.8876 (2) Å] . The bis(diphenylphosphanyl)hexane ligand bridges the Ru—Ru bond. Each phosphane-substituted Ru atom bears one equatorial and two axial terminal carbonyl ligands, whereas the unsubstituted Ru atom bears two equatorial and two axial terminal carbonyl ligands. The dihedral angles between the benzene rings attached to each P atom are 72.75 (7) and 82.02 (7)°. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond involving a methylene group of the phosphane ligand and an axial carbonyl O atom, which generates an S(6) ring motif. In the crystal, molecules are linked via C—H⋯O hydrogen bonds into layers parallel to (100).

Related literature

For general background to triangulo-triruthenium clusters with structures of the general type Ru₃(CO)₁₀ L (where L is a group 15 bidentate ligand), see: Bruce et al. (1982 ▶); Coleman et al. (1984 ▶); Teoh et al. (1990 ▶); Diz et al. (2001 ▶); Shawkataly et al. (2006 ▶, 2011 ▶); Churchill et al. (1977 ▶). For the preparation of the title compound, see: Bruce et al. (1983 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

[Ru₃(C₃₀H₃₂P₂)(CO)₁₀]
M _r = 1037.81
Monoclinic,
a = 13.4836 (6) Å
b = 21.270 (1) Å
c = 16.1025 (6) Å
β = 122.295 (3)°
V = 3903.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.29 mm⁻¹
T = 100 K
0.51 × 0.26 × 0.11 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.562, T _max = 0.869
53262 measured reflections
14125 independent reflections
12773 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.019
wR(F ²) = 0.046
S = 1.04
14125 reflections
496 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.58 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 datablock(s) global, I. DOI: 10.1107/S1600536812014614/sj5228sup1.cif

e-68-0m629-sup1.cif^{(48KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812014614/sj5228Isup2.hkl

e-68-0m629-Isup2.hkl^{(690.5KB, 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
C9—H9A⋯O3ⁱ	0.93	2.48	3.3421 (17)	154
C14—H14A⋯O6	0.97	2.58	3.2007 (19)	122
C20—H20A⋯O6ⁱ	0.93	2.59	3.495 (2)	164
C21—H21A⋯O9ⁱⁱ	0.93	2.51	3.329 (2)	147

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

Acknowledgments

ObS would like to thank Universiti Sains Malaysia (USM) for the Research University Grant No. 1001/PJJAUH/811188. SSS thanks USM for the award of a USM fellowship and for a scholarship under the Postgraduate Research Grant Scheme (PRGS) No. 1001/PJJAUH/834064. HKF thanks USM for the Research University Grant No. 1001/PFIZIK/811160.

supplementary crystallographic information

Comment

Synthesis and structural reports on substitutued triangulo-triruthenium clusters with group 15 ligands are of interest because of the observed structural variations and their potential catalytic activity. There are several reports of substituted derivatives, of the type Ru₃(CO)₁₀(L)[where L= bidentate phosphine ligand] (Coleman et al., 1984; Bruce et al., 1982; Teoh et al., 1990; Diz et al., 2001; Shawkataly et al., 2006, 2011).

The title triangulo-triruthenium(0) compound, [Ru₃(CO)₁₀(Ph₂P(CH₂)₆PPh₂)], contains triangle of singly bonded Ru atoms. These type of structures are derived from that of [Ru₃(CO)₁₂] (Churchill et al., 1977) by replacement of an equatorial carbonyl group on each of two Ru atoms by the Ph₂P groups of the diphosphane ligands. The phosphane bridged Ru-Ru distance [Ru2—Ru3 = 2.9531 (2) Å ] is significantly longer than the non-bridged Ru-Ru distances [Ru1 —Ru2 = 2.8842 (2) Å and Ru1 — Ru3 = 2.8876 (2) Å]. The bis(diphenylphosphanyl) hexane ligand bridges the Ru2– Ru3 bond. These Ru-Ru distances 2.8842 (2), 2.8876 (2) and 2.9531 (2) Å agree well with those observed in Ru₃(CO)₁₀Ph₂P(CH₂)₂PPh₂ (2.847 (1), 2.855 (1) and 2.856 (1) Å) (Bruce et al., 1982) andRu₃(CO)₁₀(F-dppe) [where F-dppe = bis(perfluoro-diphenylphosphanyl)ethane] (2.842 (4), 2.849 (4) and 2.868 (4) Å) (Diz et al., 2001) whereby the longest Ru-Ru bond is bridged by the bidentate phosphane ligand. The Ru1 atom carries two equatorial and two axial terminal carbonyl ligands whereas the Ru2 and Ru3 atoms each carries one equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings (C1–C6/C7–C12 and C19–C24/C25–C30) are 72.75 (7) and 82.02 (7)°, respectively. The molecular structure is stabilized by an intramolecular C14–H14A···O6 (Table 1) hydrogen bond, which generates an S(6) ring motif (Fig. 1, Bernstein et al., 1995).

In the crystal structure, Fig. 2, molecules are linked via intermolecular C9–H9A···O3, C20–H20A···O6 and C21–H21A···O9 hydrogen bonds (Table 1) into two-dimensional planes parallel to (100).

Experimental

All manipulations were performed under a dry, oxygen-free nitrogen atmosphere using standard Schlenk techniques. Tetrahydrofuran was dried over sodium and distilled from sodium benzophenone ketyl under nitrogen. The Ru₃(CO)₁₂ (Aldrich) and Ph₂P(CH₂)₆PPh₂ (Strem Chemicals) were used as received. Ru₃(CO)₁₀(Ph₂P(CH₂)₆PPh₂) was prepared by a reported procedure (Bruce et al., 1983). The title compound was obtained by reacting equimolar quantities of Ru₃(CO)₁₂ with Ph₂P(CH₂)₆PPh₂ in 25 ml THF. Crystals suitable for X-ray diffraction were grown by slow solvent/solvent diffusion of CH₃OH into CH₂Cl₂.