[μ-Bis(di-o-tolyl­phosphan­yl)methane-1:2κ2 P:P′]deca­carbonyl-1κ3 C,2κ3 C,3κ4 C-triangulo-triruthenium(0)–methanol (8/1)

Omar bin Shawkataly; Imthyaz Ahmed Khan; H A Hafiz Malik; Chin Sing Yeap; Hoong-Kun Fun

doi:10.1107/S1600536811000791

. 2011 Jan 15;67(Pt 2):m197–m198. doi: 10.1107/S1600536811000791

[μ-Bis(di-o-tolylphosphanyl)methane-1:2κ² P:P′]decacarbonyl-1κ³ C,2κ³ C,3κ⁴ C-triangulo-triruthenium(0)–methanol (8/1)

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

PMCID: PMC3051575 PMID: 21522864

Abstract

The asymmetric unit of the title compound, [Ru₃(C₂₉H₃₀P₂)(CO)₁₀].1/8CH₃OH, contains two triangulo-triruthenium molecules with similar configurations and a methanol solvent molecule (fractional site occupancy for the latter = 0.25). The bis(di-o-tolylphosphanyl)methane ligand bridges an Ru—Ru bond and its P atoms are equatorial with respect to the Ru₃ triangle. The phosphine-substituted Ru atoms each bear one equatorial and two axial terminal carbonyl ligands whereas the unsubstituted Ru atom carries two equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings attached to each P atom are 76.26 (13) and 74.76 (15)° for the first molecule and 77.21 (13) and 75.68 (14)° for the second. In the crystal, molecules are linked into [001] chains via intermolecular C—H⋯O hydrogen bonds. Weak intermolecular C—H⋯π interactions also occur.

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 ▶). For the synthesis of bis(di-o-tolylphosphanyl)methane, see: Filby et al. (2006 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

8[Ru₃(C₂₉H₃₀P₂)(CO)₁₀]·CH₄O
M _r = 8222.28
Monoclinic,
a = 22.7156 (13) Å
b = 19.9023 (11) Å
c = 18.4979 (10) Å
β = 106.561 (1)°
V = 8015.8 (8) Å³
Z = 1
Mo Kα radiation
μ = 1.25 mm⁻¹
T = 100 K
0.23 × 0.10 × 0.06 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.758, T _max = 0.932
107136 measured reflections
28473 independent reflections
20091 reflections with I > 2σ(I)
R _int = 0.056

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.082
S = 1.03
28473 reflections
990 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −0.72 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/S1600536811000791/hb5784sup1.cif

e-67-0m197-sup1.cif^{(61.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811000791/hb5784Isup2.hkl

e-67-0m197-Isup2.hkl^{(1.4MB, hkl)}

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

Table 1. Selected bond lengths (Å).

Ru1A—P1A	2.3451 (7)
Ru2A—P2A	2.3422 (7)
Ru1B—P1B	2.3450 (7)
Ru2B—P2B	2.3459 (7)

Open in a new tab

Table 2. Hydrogen-bond geometry (Å, °).

Cg1 is centroid of the C14A–C19A benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11B—H11B⋯O1Bⁱ	0.93	2.54	3.251 (3)	134
C24A—H24A⋯O5Aⁱⁱ	0.93	2.49	3.240 (4)	138
C29A—H29B⋯Cg1	0.96	2.96	3.702 (4)	135

Open in a new tab

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

The asymmetry unit of title compound consists of two molecule of triangulo-triruthenium complex (A & B) and one-quater molecule of methanol solvent (Fig. 1). The bis(di-o-tolylphosphanyl)methane ligand bridges the Ru1–Ru2 bond. The phosphine ligand is equatorial with respect to the Ru triangle. The Ru1 and Ru2 atoms each carries one equatorial and two axial terminal carbonyl ligands whereas the Ru3 atom carries two equatorial and two axial terminal carbonyl ligands. The dihedral angles between the two benzene rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 76.26 (13) and 74.76 (15)° in molecule A for the two diphenylphosphanyl groups respectively whereas these angles are 77.21 (13) and 75.68 (14)° in molecule B.

In the crystal, the molecules are linked into one-dimensional chains along c axis via intermolecular C11B—H11B···O1B and C24A—H24A···O5A hydrogen bonds (Fig. 2, Table 1). Weak intermolecular C—H···π interactions (Table 1) consolidate the packing.

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. Bis(di-o-tolylphosphanyl)methane (Filby et al., 2006) was prepared by reported procedure. Equimolar quantities of Ru₃(CO)₁₂ and bis(di-o-tolylphosphanyl)methane were stirred in THF (25 ml) under nitrogen. About 0.2 ml of diphenylketyl radical anion initiator was introduced into the reaction mixture under a current of nitrogen. The reaction mixture turned intense red. After 10 minutes of stirring the solvent was removed under vacuum. The reaction mixture was separated by TLC (acetone: hexane, 10:90) three bands appeared. The major band (red) was separated and characterized. Orange needles of the title compound were grown by slow solvent / solvent diffusion of CH₃OH into CH₂Cl₂.