(Carbonyl-1κC)bis­[2,3(η5)-cyclo­penta­dien­yl][μ3-(S-methyl trithio­carbonato)methylidyne-1:2:3κ4 C,S′′:C:C](triphenyl­phosphine-1κP)(μ3-sulfido-1:2:3κ3 S)dicobalt(II)iron(II) trifluoro­methane­sulfonate

Anthony R Manning; C John McAdam; Anthony J Palmer; Jim Simpson

doi:10.1107/S1600536808008970

. 2008 Apr 10;64(Pt 5):m635–m636. doi: 10.1107/S1600536808008970

(Carbonyl-1κC)bis[2,3(η⁵)-cyclopentadienyl][μ₃-(S-methyl trithiocarbonato)methylidyne-1:2:3κ⁴ C,S′′:C:C](triphenylphosphine-1κP)(μ₃-sulfido-1:2:3κ³ S)dicobalt(II)iron(II) trifluoromethanesulfonate

Anthony R Manning ^a, C John McAdam ^b, Anthony J Palmer ^a, Jim Simpson ^b,^*

PMCID: PMC2961332 PMID: 21202187

Abstract

The asymmetric unit of the title compound, [FeCo₂(C₅H₅)₂(C₃H₃S₃)S(C₁₈H₁₅P)(CO)]CF₃SO₃, consists of a triangular irondicobalt cluster cation and a trifluoromethanesulfonate anion. In the cation, the FeCo₂ triangle is symmetrically capped on one face by an S atom and on the other by a C atom linked to a methyl trithiocarbonate residue that bridges the Fe—C bond. Each Co atom carries a cyclopentadienyl ligand while the Fe atom coordinates to one carbonyl and one triphenylphosphine ligand. In the crystal structure, the cation is linked to the anion by a number of weak non-classical C—H⋯O and C—H⋯F hydrogen bonds and weak S⋯O (3.317 Å) and S⋯F (3.198 Å) interactions. The structure is further stabilized by additional intermolecular C—H⋯O, C—H⋯F and O⋯O (2.942 Å) contacts, together with an unusual S⋯π(Cp) interaction (S⋯centroid distance = 3.385 Å), generating an extended network.

Related literature

For the preparation of the title compound, see: Manning et al. (2003 ▶). For reference structural data, see: Allen et al. (1987 ▶, 2002 ▶). For related sulfur- and carbon-capped triangular FeCo₂ structures, see: Manning, O’Dwyer et al, (1995 ▶, 1998 ▶, 1999 ▶); Manning, Palmer et al. (1998 ▶). For related literature, see: Ringer et al. (2007 ▶).

Experimental

Crystal data

[FeCo₂(C₅H₅)₂(C₃H₃S₃)S(C₁₈H₁₅P)(CO)]CF₃SO₃
M _r = 910.53
Monoclinic,
a = 11.0403 (6) Å
b = 29.2183 (14) Å
c = 10.9040 (5) Å
β = 100.664 (3)°
V = 3456.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 1.77 mm⁻¹
T = 91 (2) K
0.18 × 0.06 × 0.06 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.717, T _max = 0.899
36119 measured reflections
5502 independent reflections
4297 reflections with I > 2σ(I)
R _int = 0.081

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.067
S = 1.03
5502 reflections
443 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker 2006 ▶); cell refinement: APEX2 and SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶) and TITAN2000 (Hunter & Simpson, 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and TITAN2000; molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97, enCIFer (Allen et al., 2004 ▶) and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808008970/hb2713sup1.cif

e-64-0m635-sup1.cif^{(30.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808008970/hb2713Isup2.hkl

e-64-0m635-Isup2.hkl^{(269.4KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Co2—S1	2.1275 (9)
Co1—S1	2.1564 (9)
Fe1—S1	2.1836 (9)
Fe1—C1	1.891 (3)
Fe1—Co1	2.5035 (6)
Fe1—Co2	2.6149 (6)
Co1—C1	1.867 (3)
Co1—Co2	2.4153 (6)
Co2—C1	1.880 (3)

Open in a new tab

Co2—S1—Co1	68.64 (3)
Co2—S1—Fe1	74.67 (3)
Co1—S1—Fe1	70.45 (3)
Co1—C1—Co2	80.27 (13)
Co1—C1—Fe1	83.54 (13)
Co2—C1—Fe1	87.81 (13)

Open in a new tab

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3A⋯O2	0.98	2.56	3.477 (4)	156
C3—H3C⋯F3	0.98	2.62	3.297 (4)	127
C11—H11⋯O3	0.95	2.41	3.293 (4)	154
C21—H21⋯O2	0.95	2.64	3.588 (4)	174
C21—H21⋯O3	0.95	2.64	3.235 (4)	121
C13—H13⋯O1ⁱ	0.95	2.42	3.288 (4)	152
C14—H14⋯F1ⁱ	0.95	2.56	3.248 (4)	129
C35—H35⋯O1ⁱⁱ	0.95	2.53	3.283 (4)	136
C24—H24⋯O2ⁱⁱⁱ	0.95	2.49	3.298 (4)	143

Open in a new tab

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

Acknowledgments

We thank the New Zealand Foundation for Research Science and Technology for a Postdoctoral Fellowship to CJM, and the University of Otago for the purchase of the diffractometer.

supplementary crystallographic information

Comment

The title compound (I) was first reported and characterized by us (Manning et al., 2003), as part of a study into the reaction of carbon disulfide with the µ₃-CS cluster [{Co(η⁵-C₅H₅)}₂{Fe(CO)(PPh₃)}(µ₃-S)(µ₃-CS)]. The product from this reaction, [{Co(η⁵-C₅H₅)}₂{Fe(CO)(PPh₃)}(µ₃-S)(µ₃-C₂S₃)], reacted with alkylating agents MeX to give [{Co(η⁵-C₅H₅)}₂{Fe(CO)(PPh₃)}(µ₃-S)(µ₃-C₂S₃Me)]\ ⁺[X]^- salts. The compound with [X]^- = I^- was characterized crystallographically in the initial report. Since then crystals of the compound (I) where [X]^- is trifluoromethanesulfonate have come to hand allowing us to determine the effect of the counter-anion on the unusual structure of the cation.

The asymmetric unit of (I), C₃₂H₂₈OPS₄FeCo₂⁺, CO₃F₃S^-, consists of a bicapped iron-dicobalt cluster cation and a trifluoromethanesulfonate anion (Fig. 1). The structure of the cation in (I) is very similar to that of the cation in the previously reported iodide salt [{Co(η⁵-C₅H₅)}₂{Fe(CO)(PPh₃)}(µ₃-S)(µ₃-C₂S₃Me)][I], Manning et al. (2003). The bond lengths and angles in the cations, (Table 1) are comparable in both structures. They also confirm our suggestion that the bonding within the Fe—S—C(SMe)-S—C metallocycle is delocalized. Bond distances and angles in the anion are also normal (Allen et al., 1987).

In the crystal structure the cation is linked to the anion in the asymmetric unit by a number of weak non-classical C—H···O and C—H···F hydrogen bonds and weak S···O and F···O interactions. A feature of the packing is an intermolecular S···π(Cp) interaction involving the capping S1 atom and the C21···C25 cyclopentadiene ring of an adjacent molecule (Fig. 2), with an S···Cgⁱ distance of 3.385Å and a mean S1···Cg···Cn angle of 89.9° (Cg is the centroid of the C21···C25 cyclopentadiene ring and n = 21···25; symmetry code i = x, 3/2 - y, 1/2 + z). Such interactions between S atoms and benzene rings are common, 1781 examples with S···Cg distances in the range 3.0 ··· 3.7 Å (mean 3.54 Å) and S1···Cg···Cn angles in the range 60···120° (mean 90.0°) in the Cambridge database Ver 5.29 to January 2008 (Allen et al., 2004). They are also important in determining protein folding interactions in biochemistry (Ringer et al., 2007). In contrast however, the database reveals only 194 similar interactions involving five-membered aromatic rings with the same distance and angle limitations (mean S···Cg distance 3.62 Å, S1···Cg···Cn angle 89.9), many of which involve cyclopentadiene rings in transition metal organometallic complexes.

The structure is further stabilized by additional intermolecular C—H···O, C—H···F and O···O contacts which generate an extended network (Table 2). Pairs of cluster cations, interleave with trifluoromethylsulphonate cations to form interlinked columns down the c axis (Fig. 3).

For related sulfur and carbon capped triangular FeCo₂ structures see Manning, O'Dwyer et al., (1995, 1998, 1999); Manning, Palmer et al., (1998).

Experimental

The title compound was prepared from the room temperature reaction of methyl trifluoromethanesulfonate with [{Co(η⁵-C₅H₅)}₂{Fe(CO)(PPh₃)}(µ₃-S)(µ₃-C₂S₃)], Manning et al. (2003), with X-ray quality crystals grown from dichloromethane layered with methanol.