(μ-4-Methyl­benzene­thiol­ato-κ2 S:S)bis­[carbon­yl(η5-cyclo­penta­dien­yl)molybdenum(II)]

Richard Chee Seng Wong; Mei Lee Ooi; Seik Weng Ng

doi:10.1107/S1600536808010751

. 2008 Apr 23;64(Pt 5):m695. doi: 10.1107/S1600536808010751

(μ-4-Methylbenzenethiolato-κ² S:S)bis[carbonyl(η⁵-cyclopentadienyl)molybdenum(II)]

Richard Chee Seng Wong ^a, Mei Lee Ooi ^a, Seik Weng Ng ^a,^*

PMCID: PMC2961228 PMID: 21202229

Abstract

The asymmetric unit of the title compound, [Mo₂(C₅H₅)₂(C₇H₇S)₂(CO)₂], consists of two half-molecules, each molecule lying on a centre of symmetry. The thiolate groups function as bridges between the Mo^II atoms, which adopt a quasi-octahedral geometry. In the octahedral environment the two ligating S atoms are in a cis arrangement.

Related literature

For related literature on unsubstituted [MoCp(CO)(μ-SC₆H₅)]₂, see: Song et al. (1997 ▶). The 4-methyl-substituted compound was characterized spectroscopically, see: Benson et al. (1980 ▶).

Experimental

Crystal data

[Mo₂(C₅H₅)₂(C₇H₇S)₂(CO)₂]
M _r = 624.45
Monoclinic,
a = 13.245 (2) Å
b = 10.135 (1) Å
c = 18.042 (2) Å
β = 104.901 (2)°
V = 2340.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 1.27 mm⁻¹
T = 100 (2) K
0.06 × 0.06 × 0.06 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.758, T _max = 0.928
14384 measured reflections
5374 independent reflections
3915 reflections with I > 2σ(I)
R _int = 0.048

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.104
S = 1.03
5374 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 2.60 e Å⁻³
Δρ_min = −1.77 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808010751/ci2579sup1.cif

e-64-0m695-sup1.cif^{(30.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808010751/ci2579Isup2.hkl

e-64-0m695-Isup2.hkl^{(263.2KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Mo1—S1	2.424 (1)
Mo1—S1ⁱ	2.425 (1)
Mo2—S2	2.430 (1)
Mo2—S2ⁱⁱ	2.419 (1)

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

Acknowledgments

The authors thank the Science Fund MOSTI (grant No. 03-01-03-SF0209) for funding this study, and the University of Malaya for the purchase of the diffractometer.

supplementary crystallographic information

Comment

The title compound was characterized spectroscopically in a study on [MoCp(CO)(µ-SAr]₂ type of compounds. The compound was synthesized by treating MoClCp(CO)₃ with 4-tolyl mercaptan (Benson et al., 1980). We have obtained the title compound (Fig. 1) as the unexpected product in the reaction of [(η5-C₅H₅)Mo(CO)₂]₂ with deuterated o-P(PhSCD₃)₃. Under the conditions of the reaction, the ortho-SD₃ groups of the phosphine have been rearranged to the para position. The rearrangement is then followed by an exchange of the deuterium atoms by hydrogen atoms; the absence of deuterium in the compound is confirmed by ¹H NMR spectroscopic analysis.

Experimental

A reddish-brown suspension of [(η5-C₅H₅)Mo(CO)₂]₂ (100 mg, 0.23 mmol) and an equivalent quantity of the deuterated phosphine, o-P(PhSCD₃)₃ (94 mg, 0.23 mol), was heated at 383 K for 14.5 h under argon. The mixture was filtered and then absorbed onto Celite (1.5 g). The slurry was evacuated to dryness and loaded onto a silica gel column (9.5 cm x 2.0 cm) in n-hexane. The title compound was eluted with n-hexane-toluene (1:4, 50 ml) as a greenish-brown fraction (60.0 mg, 0.096 mmol, 40% yield). The dichroic compound was recrystallized from an n-hexane-toluene mixture and crystals were isolated after 2 d.