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

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

doi:10.1107/S1600536809047977

. 2009 Nov 21;65(Pt 12):m1626–m1627. doi: 10.1107/S1600536809047977

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

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

PMCID: PMC2972057 PMID: 21578646

Abstract

In the title triangulo-triruthenium compound, [Ru₃(C₂₅H₂₂As₂)(C₁₈H₃₃P)(CO)₉], the bis(diphenylarsino)methane ligand bridges an Ru—Ru bond and the monodentate phosphine ligand bonds to the third Ru atom. Both the phosphine 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. All three cyclohexane rings are disordered over two positions with site occupancies of 0.628 (6) and 0.372 (6). The mean planes of these three phosphine-substituted cyclohexane rings make dihedral angles of 53.0 (8), 68.3 (6) and 89.9 (7)° (major components), and 46.7 (14), 41.3 (11) and 75.8 (10)° (minor components) with each other. The dihedral angles between the two phenyl rings are 85.0 (2) and 88.1 (2)° for the two diphenylarsino groups. Two cyclohexane rings adopt a chair conformation whereas the other adopts a slightly twisted chair conformation for the major components; these conformations are similiar for the minor components. Intramolecular C—H⋯O hydrogen bonds stabilize the molecular structure. In the crystal packing, the molecules are linked together into chains via intermolecular C—H⋯O hydrogen bonds down the a axis. Weak intermolecular C—H⋯π interactions further stabilize the crystal structure.

Related literature

For general background to triangulo-triruthenium derivatives, see: Bruce et al. (1985 ▶, 1988a ▶,b ▶); Shawkataly et al. (1998 ▶, 2004 ▶). For related structures, see: Shawkataly et al. (2009a ▶,b ▶). For the synthesis of bis(diphenylarsino)methane, see: Bruce et al. (1983 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). graphic file with name e-65-m1626-scheme1.jpg

Experimental

Crystal data

[Ru₃(C₂₅H₂₂As₂)(C₁₈H₃₃P)(CO)₉]
M _r = 1307.98
Orthorhombic,
a = 15.6489 (2) Å
b = 20.9223 (3) Å
c = 31.3447 (5) Å
V = 10262.6 (3) Å³
Z = 8
Mo Kα radiation
μ = 2.24 mm⁻¹
T = 100 K
0.30 × 0.14 × 0.04 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.555, T _max = 0.922
62224 measured reflections
11768 independent reflections
8148 reflections with I > 2σ(I)
R _int = 0.092

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.099
S = 1.01
11768 reflections
728 parameters
379 restraints
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.61 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/S1600536809047977/sj2677sup1.cif

e-65-m1626-sup1.cif^{(55.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809047977/sj2677Isup2.hkl

e-65-m1626-Isup2.hkl^{(575.5KB, 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
C31A—H31B⋯O8	0.97	2.56	3.481 (17)	159
C32A—H32A⋯O9	0.98	2.47	3.157 (14)	127
C43A—H43B⋯O9ⁱ	0.97	2.18	2.954 (10)	135
C5—H5A⋯Cg1ⁱⁱ	0.93	2.94	3.728 (5)	144
C10—H10A⋯Cg2ⁱⁱⁱ	0.93	2.90	3.651 (5)	139
C16—H16A⋯Cg2^iv	0.93	2.96	3.718 (5)	140
C22—H22A⋯Cg1^v	0.93	2.82	3.608 (5)	143
C41B—H41D⋯Cg3ⁱⁱ	0.97	2.62	3.420 (14)	140

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) . Cg1, Cg2 and Cg3 are the centroids of the C7–C12, C20–C25 and C1–C6 phenyl rings, respectively.

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

Tri-angulotriruthenium 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 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 tri-angulotriruthenium-carbonyl clusters containing mixed P/As and P/Sb ligands (Shawkataly et al., 1998, 2004, 2009a,b). Herein we report the synthesis and structure of Ru₃(C₁₈H₃₃P)(C₂₅H₂₂As₂)(CO)₉.

The bond lengths and angles of title compound (Fig. 1 & 2) are comparable to those in related structures (Shawkataly et al., 2009a,b). 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. All three cyclohexane rings are disordered over two positions with site occupancies of 0.628 (6) and 0.372 (6). Only the C41, C42 and C43 atoms in the C38-C43 ring are disordered. The mean planes of these three phosphine-substituted cyclohexane rings make dihedral angles (C26–C31/C32–C37, C26–C31/C38–C43 and C32–C37/C38–C43) of 53.0 (8), 68.3 (6) and 89.9 (7)° with each other respectively for the major components and 46.7 (14), 41.3 (11) and 75.8 (10)° for the minor components. The dihedral angles between the two phenyl rings (C1–C6/C7–C12 and C14–C19/C20–C25) are 85.0 (2) and 88.1 (2)° for the two diphenylarsino groups respectively. Four cyclohexane rings adopt a chair conformation with puckering amplitude Q = 0.555 (17) Å, θ = 0.0 (18)°, φ = 191 (176)° for C26A–C32A ring, Q = 0.572 (18) Å, θ = 180.0 (18)°, φ = 235 (45)° for C32A–C37A ring, Q = 0.52 (3) Å, θ = 10 (3)°, φ = 120 (26)° for C26B–C31B ring and Q = 0.58 (3) Å, θ = 177 (3)°, φ = 90 (166)° for C32B–C37B ring. The other two cyclohexane rings (C38–C43A and C38–C43B) adopt a slightly twisted chair conformation with Q = 0.545 (8) Å, θ = 159.3 (8)°, φ = 137 (2)° and Q = 0.465 (12) Å, θ = 27.0 (14)°, φ = 307 (3)°, respectively (Cremer & Pople, 1975).

In the crystal packing (Fig. 3), intramolecular C31—H31B···O8 and C32—H32A···O9 hydrogen bonds stabilize the molecular structure and the molecules are linked together into chains via intermolecular C43—H43B···O9 hydrogen bonds down a axis. Weak intermolecular C—H···π interactions further stabilize the crystal structure (Table 1).

Experimental

The reactions were conducted under an atmosphere of nitrogen using standard Schlenk techniques and hexane-dried over sodium metal. Tricyclohexylphosphine (Strem Chemicals) used as received and bis(diphenylarsino)methane (Bruce et al., 1983) was prepared by the reported procedure. The title compound was obtained by refluxing equimolar quantities of Ru₃(CO)₁₀(µ-Ph₂AsCH₂AsPh₂) (105.5 mg, 0.1 mmol) and tricyclohexylphosphine (27.8 mg, 0.1 mmol) in hexane under nitrogen atmosphere. Crystals suitable for X-ray diffraction were grown by slow solvent / solvent diffusion of CH₃OH into CHCl₃.