(Carbonyl-1κC)bis­[2,3(η5)-cyclo­penta­dien­yl][μ3-(S-methyl trithio­carbonato)methylidyne-1:2:3κ4C,S′′:C:C](triphenyl­phosphine-1κP)(μ3-sulfido-1:2:3κ3S)dicobalt(II)iron(II) trifluoro­methane­sulfonate

Manning, A.R.; McAdam, C.J.; Palmer, A.J.; Simpson, J.

doi:10.1107/S1600536808008970

Volume 64
Part 5
Pages m635-m636
May 2008

Received 31 March 2008
Accepted 2 April 2008
Online 10 April 2008

Key indicators
Single-crystal X-ray study
T = 91 K
Mean (C-C) = 0.005 Å
R = 0.031
wR = 0.068
Data-to-parameter ratio = 12.4
Details

(Carbonyl-1C)bis[2,3(⁵)-cyclopentadienyl][₃-(S-methyl trithiocarbonato)methylidyne-1:2:3⁴C,S'':C:C](triphenylphosphine-1P)(₃-sulfido-1:2:3³S)dicobalt(II)iron(II) trifluoromethanesulfonate

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

^aDepartment of Chemistry, University College Dublin, Belfield, Dublin 4, Ireland, and ^bDepartment of Chemistry, University of Otago, PO Box 56, Dunedin, New Zealand
Correspondence e-mail: jsimpson@alkali.otago.ac.nz

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-HO and C-HF hydrogen bonds and weak SO (3.317 Å) and SF (3.198 Å) interactions. The structure is further stabilized by additional intermolecular C-HO, C-HF and OO (2.942 Å) contacts, together with an unusual S [pi] (Cp) interaction (Scentroid 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, P 2₁ /c
a = 11.0403 (6) Å
b = 29.2183 (14) Å
c = 10.9040 (5) Å
= 100.664 (3)°
V = 3456.7 (3) Å³
Z = 4
Mo K radiation
= 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 > 2(I)
R_int = 0.081

Refinement

R[F² > 2(F²)] = 0.031
wR(F²) = 0.067
S = 1.03
5502 reflections
443 parameters
H-atom parameters constrained
_max = 0.38 e Å^-3
_min = -0.35 e Å^-3

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)

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)

Table 2
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
C3-H3AO2	0.98	2.56	3.477 (4)	156
C3-H3CF3	0.98	2.62	3.297 (4)	127
C11-H11O3	0.95	2.41	3.293 (4)	154
C21-H21O2	0.95	2.64	3.588 (4)	174
C21-H21O3	0.95	2.64	3.235 (4)	121
C13-H13O1ⁱ	0.95	2.42	3.288 (4)	152
C14-H14F1ⁱ	0.95	2.56	3.248 (4)	129
C35-H35O1ⁱⁱ	0.95	2.53	3.283 (4)	136
C24-H24O2ⁱⁱⁱ	0.95	2.49	3.298 (4)	143
Symmetry codes: (i) x, y, z+1; (ii) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[x, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

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 data and figures for this paper are available from the IUCr electronic archives (Reference: HB2713 ).

Acknowledgements

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.

References

Allen, F. H. (2002). Acta Cryst. B58, 380-388.
Allen, F. H., Johnson, O., Shields, G. P., Smith, B. R. & Towler, M. (2004). J. Appl. Cryst. 37, 335-338.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-S19.
Bruker (2006). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
Hunter, K. A. & Simpson, J. (1999). TITAN2000. University of Otago, New Zealand.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.
Manning, A. R., McAdam, C. J., Palmer, A. J., Robinson, B. H. & Simpson, J. (2003). Dalton Trans. pp. 4472-4481.
Manning, A. R., O'Dwyer, L., McArdle, P. A. & Cunningham, D. (1995). J. Organomet. Chem. 503, C46-C47.
Manning, A. R., O'Dwyer, L., McArdle, P. A. & Cunningham, D. (1998). J. Organomet. Chem. 551, 139-149.
Manning, A. R., O'Dwyer, L., McArdle, P. A. & Cunningham, D. (1999). J. Organomet. Chem. 573, 109-120.
Manning, A. R., Palmer, A. J., McAdam, C. J., Robinson, B. H. & Simpson, J. (1998). Chem. Commun. pp. 1577-1578.
Ringer, A. L., Senenko, A. & Sherrill, C. D. (2007). Protein Sci. 16, 1-8.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7-13.

metal-organic compounds

(Carbonyl-1C)bis[2,3(5)-cyclopentadienyl][3-(S-methyl trithiocarbonato)methylidyne-1:2:34C,S'':C:C](triphenylphosphine-1P)(3-sulfido-1:2:33S)dicobalt(II)iron(II) trifluoromethanesulfonate