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Acta Cryst. (2008). E64, m635-m636    [ doi:10.1107/S1600536808008970 ]

(Carbonyl-1[kappa]C)bis[2,3([eta]5)-cyclopentadienyl][[mu]3-(S-methyl trithiocarbonato)methylidyne-1:2:3[kappa]4C,S'':C:C](triphenylphosphine-1[kappa]P)([mu]3-sulfido-1:2:3[kappa]3S)dicobalt(II)iron(II) trifluoromethanesulfonate

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

Abstract top

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...[pi](Cp) interaction (S...centroid distance = 3.385 Å), generating an extended network.

Comment top

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).

Related literature top

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 top

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.

Refinement top

The crystals were small and weakly diffracting and little useable data were obtained beyond θ = 24°. All H-atoms bound to carbon were refined using a riding model with d(C—H) = 0.95 Å, Uiso=1.2Ueq (C) for aromatic and 0.98 Å, Uiso = 1.5Ueq (C) for CH3 H atoms.

Computing details top

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

Figures top
[Figure 1] Fig. 1. The asymmetric unit of (I), with 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The unusual S···π(Cp) interaction (dotted line) in (I). The red circle represents the centroid of the C21···C25 cyclopentadiene ring.
[Figure 3] Fig. 3. Crystal packing of (I) viewed down the c axis.
(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 top
Crystal data top
[FeCo2(C5H5)2(C3H3S3)S(C18H15P)(CO)]CF3SO3F000 = 1840
Mr = 910.53Dx = 1.750 Mg m−3
Monoclinic, P21/cMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5433 reflections
a = 11.0403 (6) Åθ = 2.3–23.6º
b = 29.2183 (14) ŵ = 1.77 mm−1
c = 10.9040 (5) ÅT = 91 (2) K
β = 100.664 (3)ºIrregular fragment, black
V = 3456.7 (3) Å30.18 × 0.06 × 0.06 mm
Z = 4
Data collection top
Bruker APEXII CCD area-detector
diffractometer		5502 independent reflections
Radiation source: fine-focus sealed tube4297 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.081
T = 91(2) Kθmax = 24.2º
ω scansθmin = 2.0º
Absorption correction: multi-scan
(SADABS; Bruker, 2006)		h = −12→12
Tmin = 0.717, Tmax = 0.899k = −33→33
36119 measured reflectionsl = −12→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.067  w = 1/[σ2(Fo2) + (0.0227P)2 + 1.9058P]
where P = (Fo2 + 2Fc2)/3
S = 1.03(Δ/σ)max = 0.002
5502 reflectionsΔρmax = 0.38 e Å−3
443 parametersΔρmin = −0.35 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
[FeCo2(C5H5)2(C3H3S3)S(C18H15P)(CO)]CF3SO3V = 3456.7 (3) Å3
Mr = 910.53Z = 4
Monoclinic, P21/cMo Kα
a = 11.0403 (6) ŵ = 1.77 mm−1
b = 29.2183 (14) ÅT = 91 (2) K
c = 10.9040 (5) Å0.18 × 0.06 × 0.06 mm
β = 100.664 (3)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		5502 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2006)		4297 reflections with I > 2σ(I)
Tmin = 0.717, Tmax = 0.899Rint = 0.081
36119 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.031443 parameters
wR(F2) = 0.067H-atom parameters constrained
S = 1.03Δρmax = 0.38 e Å−3
5502 reflectionsΔρmin = −0.35 e Å−3
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.43507 (7)0.68025 (3)0.84869 (8)0.01321 (19)
Fe10.38034 (4)0.614761 (15)0.75881 (4)0.01093 (12)
Co10.59348 (4)0.647577 (15)0.79713 (4)0.01244 (12)
Co20.43989 (4)0.690431 (15)0.65645 (4)0.01123 (11)
C10.4900 (3)0.62912 (11)0.6502 (3)0.0119 (7)
S20.52197 (7)0.59798 (3)0.52361 (8)0.01445 (19)
C20.3965 (3)0.56308 (11)0.5050 (3)0.0126 (7)
S30.36348 (8)0.52579 (3)0.38030 (8)0.0195 (2)
C30.4831 (3)0.53630 (12)0.2912 (3)0.0219 (8)
H3A0.48770.56920.27470.033*
H3B0.46420.51970.21190.033*
H3C0.56240.52580.33860.033*
S40.29960 (7)0.56474 (3)0.60791 (8)0.0158 (2)
C40.4330 (3)0.57269 (12)0.8704 (3)0.0169 (8)
O40.4722 (2)0.54557 (8)0.9446 (2)0.0268 (6)
C110.7657 (3)0.65135 (13)0.7521 (3)0.0218 (9)
H110.78220.65730.67120.026*
C120.7543 (3)0.68458 (12)0.8438 (3)0.0232 (9)
H120.76080.71680.83500.028*
C130.7314 (3)0.66107 (13)0.9513 (3)0.0242 (9)
H130.72090.67481.02760.029*
C140.7270 (3)0.61407 (13)0.9253 (3)0.0249 (9)
H140.71240.59050.98070.030*
C150.7481 (3)0.60788 (13)0.8022 (3)0.0249 (9)
H150.75010.57940.76060.030*
C210.4574 (3)0.71066 (11)0.4791 (3)0.0171 (8)
H210.48800.69200.42020.021*
C220.3330 (3)0.71431 (11)0.4931 (3)0.0166 (8)
H220.26530.69880.44410.020*
C230.3258 (3)0.74476 (11)0.5918 (3)0.0173 (8)
H230.25340.75290.62240.021*
C240.4474 (3)0.76111 (11)0.6372 (3)0.0187 (8)
H240.47030.78270.70260.022*
C250.5283 (3)0.73976 (11)0.5685 (3)0.0192 (8)
H250.61490.74420.58020.023*
P10.19319 (7)0.62119 (3)0.81383 (8)0.01130 (19)
C310.1058 (3)0.66800 (11)0.7289 (3)0.0118 (7)
C320.0804 (3)0.66594 (11)0.5986 (3)0.0150 (8)
H320.10910.64070.55720.018*
C330.0139 (3)0.70032 (12)0.5291 (3)0.0185 (8)
H33−0.00510.69800.44080.022*
C34−0.0247 (3)0.73794 (12)0.5880 (3)0.0205 (8)
H34−0.07110.76140.54050.025*
C350.0044 (3)0.74128 (11)0.7162 (3)0.0192 (8)
H35−0.01990.76760.75670.023*
C360.0686 (3)0.70657 (11)0.7865 (3)0.0159 (8)
H360.08730.70920.87490.019*
C410.1856 (3)0.63076 (11)0.9778 (3)0.0130 (7)
C420.0678 (3)0.63315 (11)1.0099 (3)0.0138 (7)
H42−0.00360.63170.94630.017*
C430.0553 (3)0.63756 (11)1.1325 (3)0.0170 (8)
H43−0.02440.63991.15310.020*
C440.1591 (3)0.63864 (11)1.2259 (3)0.0157 (8)
H440.15020.64071.31070.019*
C450.2758 (3)0.63666 (11)1.1963 (3)0.0153 (8)
H450.34670.63781.26060.018*
C460.2888 (3)0.63291 (11)1.0721 (3)0.0131 (7)
H460.36880.63181.05180.016*
C510.0968 (3)0.56975 (11)0.7843 (3)0.0135 (7)
C520.0065 (3)0.56312 (12)0.6782 (3)0.0196 (8)
H52−0.01160.58690.61830.024*
C53−0.0570 (3)0.52218 (12)0.6594 (3)0.0241 (9)
H53−0.11730.51780.58600.029*
C54−0.0332 (3)0.48759 (12)0.7471 (4)0.0254 (9)
H54−0.07780.45970.73430.030*
C550.0555 (3)0.49360 (12)0.8532 (3)0.0239 (9)
H550.07130.47010.91420.029*
C560.1210 (3)0.53417 (11)0.8701 (3)0.0189 (8)
H560.18390.53780.94170.023*
S50.71566 (8)0.65888 (3)0.32134 (8)0.0176 (2)
O10.7829 (2)0.68745 (8)0.2496 (2)0.0249 (6)
O20.59310 (19)0.64632 (8)0.2590 (2)0.0201 (6)
O30.7252 (2)0.67193 (9)0.4504 (2)0.0260 (6)
C600.7989 (3)0.60449 (13)0.3295 (3)0.0221 (8)
F10.78346 (19)0.58458 (7)0.21758 (19)0.0351 (6)
F20.92021 (16)0.61032 (7)0.36923 (18)0.0264 (5)
F30.76096 (18)0.57506 (7)0.4081 (2)0.0321 (5)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0146 (4)0.0129 (5)0.0127 (4)−0.0008 (3)0.0039 (3)−0.0018 (3)
Fe10.0111 (3)0.0106 (3)0.0116 (3)−0.0004 (2)0.00340 (19)0.0001 (2)
Co10.0102 (2)0.0157 (3)0.0112 (2)−0.00022 (19)0.00134 (18)−0.00025 (19)
Co20.0121 (2)0.0103 (2)0.0113 (2)−0.00045 (19)0.00221 (18)0.00090 (19)
C10.0094 (17)0.0112 (18)0.0156 (18)0.0009 (13)0.0038 (14)0.0007 (14)
S20.0156 (4)0.0144 (5)0.0144 (4)−0.0022 (4)0.0057 (4)−0.0032 (3)
C20.0123 (17)0.0109 (18)0.0148 (18)0.0048 (14)0.0035 (14)0.0019 (14)
S30.0193 (5)0.0198 (5)0.0198 (5)−0.0038 (4)0.0044 (4)−0.0074 (4)
C30.024 (2)0.025 (2)0.017 (2)0.0017 (16)0.0063 (16)−0.0051 (16)
S40.0140 (4)0.0157 (5)0.0188 (5)−0.0029 (4)0.0055 (4)−0.0033 (4)
C40.0149 (19)0.019 (2)0.019 (2)0.0005 (15)0.0081 (15)−0.0054 (17)
O40.0319 (15)0.0215 (15)0.0268 (15)0.0092 (12)0.0052 (12)0.0096 (12)
C110.0101 (18)0.043 (3)0.0125 (19)−0.0021 (16)0.0019 (14)0.0019 (17)
C120.0089 (18)0.024 (2)0.034 (2)−0.0051 (15)−0.0029 (16)0.0023 (18)
C130.0138 (19)0.044 (3)0.0131 (19)0.0004 (17)−0.0028 (15)−0.0050 (17)
C140.0151 (19)0.033 (2)0.023 (2)0.0009 (17)−0.0054 (16)0.0120 (17)
C150.0099 (18)0.033 (2)0.030 (2)0.0071 (16)−0.0024 (16)−0.0062 (18)
C210.024 (2)0.0151 (19)0.0141 (19)0.0052 (15)0.0093 (15)0.0054 (15)
C220.0197 (19)0.0156 (19)0.0129 (18)0.0019 (15)−0.0014 (15)0.0047 (15)
C230.0200 (19)0.0093 (18)0.023 (2)0.0055 (15)0.0046 (15)0.0030 (15)
C240.026 (2)0.0075 (18)0.020 (2)0.0002 (15)−0.0021 (16)0.0012 (14)
C250.0144 (18)0.018 (2)0.025 (2)−0.0035 (15)0.0024 (15)0.0113 (16)
P10.0109 (4)0.0114 (5)0.0117 (5)−0.0007 (4)0.0025 (3)−0.0005 (4)
C310.0084 (17)0.0115 (18)0.0165 (19)−0.0022 (14)0.0050 (14)0.0015 (14)
C320.0137 (18)0.0134 (18)0.0170 (19)−0.0028 (14)0.0005 (15)−0.0010 (15)
C330.0173 (19)0.023 (2)0.0133 (18)−0.0009 (16)−0.0017 (15)0.0038 (15)
C340.0126 (18)0.024 (2)0.024 (2)0.0012 (15)−0.0001 (15)0.0086 (16)
C350.0207 (19)0.0122 (19)0.026 (2)0.0035 (15)0.0072 (16)−0.0013 (16)
C360.0184 (19)0.0155 (19)0.0151 (18)−0.0010 (15)0.0066 (15)−0.0001 (15)
C410.0133 (18)0.0101 (18)0.0168 (18)−0.0008 (14)0.0057 (14)0.0011 (14)
C420.0125 (18)0.0143 (19)0.0138 (18)−0.0005 (14)0.0004 (14)−0.0007 (14)
C430.0180 (19)0.0154 (19)0.021 (2)−0.0017 (15)0.0115 (16)0.0017 (15)
C440.024 (2)0.0146 (19)0.0096 (17)−0.0041 (15)0.0059 (15)−0.0016 (14)
C450.0166 (19)0.0146 (19)0.0132 (18)−0.0028 (15)−0.0012 (15)0.0022 (14)
C460.0118 (17)0.0112 (18)0.0177 (19)−0.0010 (14)0.0059 (14)−0.0019 (14)
C510.0084 (17)0.0157 (19)0.0188 (19)0.0009 (14)0.0088 (14)−0.0008 (15)
C520.0192 (19)0.018 (2)0.021 (2)−0.0019 (16)0.0028 (15)0.0031 (16)
C530.0167 (19)0.024 (2)0.030 (2)−0.0065 (16)−0.0004 (16)−0.0021 (18)
C540.022 (2)0.016 (2)0.040 (2)−0.0047 (16)0.0102 (18)−0.0036 (18)
C550.025 (2)0.017 (2)0.030 (2)0.0007 (16)0.0063 (17)0.0038 (17)
C560.0191 (19)0.017 (2)0.021 (2)−0.0005 (16)0.0035 (15)0.0013 (16)
S50.0152 (5)0.0214 (5)0.0160 (5)−0.0011 (4)0.0028 (4)0.0013 (4)
O10.0238 (14)0.0281 (15)0.0232 (14)−0.0080 (11)0.0052 (11)0.0041 (11)
O20.0150 (13)0.0223 (14)0.0216 (14)−0.0027 (10)−0.0005 (10)0.0039 (11)
O30.0248 (14)0.0368 (16)0.0171 (14)0.0012 (12)0.0054 (11)−0.0063 (12)
C600.015 (2)0.034 (2)0.018 (2)0.0016 (17)0.0050 (16)0.0002 (17)
F10.0359 (13)0.0377 (14)0.0288 (13)0.0105 (11)−0.0013 (10)−0.0149 (11)
F20.0148 (11)0.0381 (13)0.0267 (12)0.0016 (9)0.0046 (9)−0.0003 (10)
F30.0258 (12)0.0291 (13)0.0442 (14)0.0049 (10)0.0136 (10)0.0168 (11)
Geometric parameters (Å, °) top
Co2—S12.1275 (9)C22—C231.410 (5)
Co1—S12.1564 (9)C22—H220.9500
Fe1—S12.1836 (9)C23—C241.425 (4)
Fe1—C41.751 (4)C23—H230.9500
Fe1—C11.891 (3)C24—C251.413 (5)
Fe1—S42.2572 (9)C24—H240.9500
Fe1—P12.2634 (10)C25—H250.9500
Fe1—Co12.5035 (6)P1—C311.824 (3)
Fe1—Co22.6149 (6)P1—C411.827 (3)
Co1—C11.867 (3)P1—C511.835 (3)
Co1—C112.052 (3)C31—C361.389 (4)
Co1—C152.056 (3)C31—C321.398 (4)
Co1—C122.060 (3)C32—C331.384 (4)
Co1—C142.079 (3)C32—H320.9500
Co1—C132.086 (3)C33—C341.380 (5)
Co1—Co22.4153 (6)C33—H330.9500
Co2—C11.880 (3)C34—C351.379 (5)
Co2—C212.065 (3)C34—H340.9500
Co2—C222.067 (3)C35—C361.385 (4)
Co2—C232.068 (3)C35—H350.9500
Co2—C252.073 (3)C36—H360.9500
Co2—C242.079 (3)C41—C461.388 (4)
C1—S21.743 (3)C41—C421.410 (4)
S2—C21.702 (3)C42—C431.375 (4)
S2—F33.198 (2)C42—H420.9500
S2—O33.317 (3)C43—C441.385 (4)
S2—S53.7879 (12)C43—H430.9500
S2—C604.032 (4)C44—C451.387 (4)
C2—S41.688 (3)C44—H440.9500
C2—S31.728 (3)C45—C461.392 (4)
S3—C31.805 (3)C45—H450.9500
C3—H3A0.9800C46—H460.9500
C3—H3B0.9800C51—C561.391 (4)
C3—H3C0.9800C51—C521.394 (4)
C4—O41.158 (4)C52—C531.382 (5)
C4—O4i4.040 (5)C52—H520.9500
O4—O4i2.941 (5)C53—C541.383 (5)
C11—C151.410 (5)C53—H530.9500
C11—C121.416 (5)C54—C551.382 (5)
C11—H110.9500C54—H540.9500
C12—C131.421 (5)C55—C561.383 (5)
C12—H120.9500C55—H550.9500
C13—C141.401 (5)C56—H560.9500
C13—H130.9500S5—O11.440 (2)
C14—C151.416 (5)S5—O31.443 (2)
C14—H140.9500S5—O21.445 (2)
C15—H150.9500S5—C601.829 (4)
C21—C221.414 (4)C60—F11.334 (4)
C21—C251.415 (5)C60—F31.335 (4)
C21—H210.9500C60—F21.340 (4)
Co2—S1—Co168.64 (3)C13—C12—Co170.94 (19)
Co2—S1—Fe174.67 (3)C11—C12—H12126.2
Co1—S1—Fe170.45 (3)C13—C12—H12126.2
C4—Fe1—C1114.96 (14)Co1—C12—H12124.9
C4—Fe1—S1105.94 (11)C14—C13—C12108.1 (3)
C1—Fe1—S186.02 (10)C14—C13—Co170.05 (19)
C4—Fe1—S495.02 (11)C12—C13—Co168.97 (19)
C1—Fe1—S484.22 (10)C14—C13—H13125.9
S1—Fe1—S4159.02 (4)C12—C13—H13125.9
C4—Fe1—P194.37 (11)Co1—C13—H13126.6
C1—Fe1—P1150.38 (10)C13—C14—C15108.2 (3)
S1—Fe1—P189.92 (3)C13—C14—Co170.6 (2)
S4—Fe1—P189.44 (3)C15—C14—Co169.12 (19)
C4—Fe1—Co188.38 (11)C13—C14—H14125.9
C1—Fe1—Co147.82 (9)C15—C14—H14125.9
S1—Fe1—Co154.27 (3)Co1—C14—H14125.9
S4—Fe1—Co1127.00 (3)C11—C15—C14108.1 (3)
P1—Fe1—Co1143.12 (3)C11—C15—Co169.8 (2)
C4—Fe1—Co2144.34 (11)C14—C15—Co170.84 (19)
C1—Fe1—Co245.92 (9)C11—C15—H15126.0
S1—Fe1—Co251.69 (3)C14—C15—H15126.0
S4—Fe1—Co2109.44 (3)Co1—C15—H15125.0
P1—Fe1—Co2110.91 (3)C22—C21—C25107.7 (3)
Co1—Fe1—Co256.263 (16)C22—C21—Co270.06 (18)
C1—Co1—C11104.89 (14)C25—C21—Co270.28 (19)
C1—Co1—C15103.48 (14)C22—C21—H21126.1
C11—Co1—C1540.14 (14)C25—C21—H21126.1
C1—Co1—C12136.54 (15)Co2—C21—H21125.1
C11—Co1—C1240.27 (14)C23—C22—C21108.9 (3)
C15—Co1—C1267.43 (14)C23—C22—Co270.08 (18)
C1—Co1—C14133.31 (14)C21—C22—Co269.91 (18)
C11—Co1—C1467.24 (14)C23—C22—H22125.6
C15—Co1—C1440.04 (14)C21—C22—H22125.6
C12—Co1—C1467.03 (14)Co2—C22—H22126.0
C1—Co1—C13170.24 (14)C22—C23—C24107.1 (3)
C11—Co1—C1367.19 (14)C22—C23—Co270.05 (18)
C15—Co1—C1366.83 (14)C24—C23—Co270.33 (18)
C12—Co1—C1340.08 (14)C22—C23—H23126.5
C14—Co1—C1339.32 (14)C24—C23—H23126.5
C1—Co1—S187.40 (10)Co2—C23—H23124.8
C11—Co1—S1150.50 (11)C25—C24—C23108.4 (3)
C15—Co1—S1162.20 (11)C25—C24—Co269.87 (19)
C12—Co1—S1114.00 (11)C23—C24—Co269.47 (18)
C14—Co1—S1122.79 (11)C25—C24—H24125.8
C13—Co1—S1102.27 (10)C23—C24—H24125.8
C1—Co1—Co250.10 (10)Co2—C24—H24126.4
C11—Co1—Co2113.13 (10)C24—C25—C21107.9 (3)
C15—Co1—Co2142.31 (11)C24—C25—Co270.35 (19)
C12—Co1—Co2110.88 (10)C21—C25—Co269.72 (19)
C14—Co1—Co2176.57 (11)C24—C25—H25126.0
C13—Co1—Co2137.37 (11)C21—C25—H25126.0
S1—Co1—Co255.12 (3)Co2—C25—H25125.5
C1—Co1—Fe148.64 (10)C31—P1—C41105.44 (15)
C11—Co1—Fe1149.80 (10)C31—P1—C51106.86 (14)
C15—Co1—Fe1122.58 (11)C41—P1—C5199.61 (15)
C12—Co1—Fe1169.27 (10)C31—P1—Fe1110.52 (11)
C14—Co1—Fe1117.35 (10)C41—P1—Fe1118.79 (11)
C13—Co1—Fe1136.90 (10)C51—P1—Fe1114.43 (11)
S1—Co1—Fe155.28 (3)C36—C31—C32118.3 (3)
Co2—Co1—Fe164.199 (18)C36—C31—P1123.5 (2)
C1—Co2—C2199.18 (14)C32—C31—P1118.1 (2)
C1—Co2—C22114.54 (13)C33—C32—C31120.8 (3)
C21—Co2—C2240.03 (12)C33—C32—H32119.6
C1—Co2—C23152.15 (13)C31—C32—H32119.6
C21—Co2—C2367.54 (13)C34—C33—C32120.1 (3)
C22—Co2—C2339.88 (13)C34—C33—H33119.9
C1—Co2—C25118.61 (14)C32—C33—H33119.9
C21—Co2—C2540.00 (13)C35—C34—C33119.6 (3)
C22—Co2—C2567.01 (13)C35—C34—H34120.2
C23—Co2—C2567.53 (13)C33—C34—H34120.2
C1—Co2—C24157.72 (14)C34—C35—C36120.6 (3)
C21—Co2—C2466.98 (14)C34—C35—H35119.7
C22—Co2—C2466.74 (13)C36—C35—H35119.7
C23—Co2—C2440.20 (12)C35—C36—C31120.5 (3)
C25—Co2—C2439.79 (13)C35—C36—H36119.7
C1—Co2—S187.93 (10)C31—C36—H36119.7
C21—Co2—S1170.52 (10)C46—C41—C42118.8 (3)
C22—Co2—S1141.40 (10)C46—C41—P1123.5 (2)
C23—Co2—S1108.56 (10)C42—C41—P1117.5 (2)
C25—Co2—S1130.76 (10)C43—C42—C41120.6 (3)
C24—Co2—S1104.29 (10)C43—C42—H42119.7
C1—Co2—Co149.63 (9)C41—C42—H42119.7
C21—Co2—Co1124.51 (9)C42—C43—C44119.9 (3)
C22—Co2—Co1160.72 (10)C42—C43—H43120.0
C23—Co2—Co1157.87 (9)C44—C43—H43120.0
C25—Co2—Co1108.60 (9)C43—C44—C45120.4 (3)
C24—Co2—Co1122.85 (9)C43—C44—H44119.8
S1—Co2—Co156.25 (3)C45—C44—H44119.8
C1—Co2—Fe146.27 (10)C44—C45—C46119.8 (3)
C21—Co2—Fe1135.74 (10)C44—C45—H45120.1
C22—Co2—Fe1120.30 (10)C46—C45—H45120.1
C23—Co2—Fe1127.53 (10)C41—C46—C45120.4 (3)
C25—Co2—Fe1164.27 (10)C41—C46—H46119.8
C24—Co2—Fe1154.27 (10)C45—C46—H46119.8
S1—Co2—Fe153.64 (3)C56—C51—C52118.2 (3)
Co1—Co2—Fe159.538 (17)C56—C51—P1117.4 (2)
S2—C1—Co1130.47 (17)C52—C51—P1124.2 (3)
S2—C1—Co2129.07 (18)C53—C52—C51120.6 (3)
Co1—C1—Co280.27 (13)C53—C52—H52119.7
S2—C1—Fe1128.84 (18)C51—C52—H52119.7
Co1—C1—Fe183.54 (13)C52—C53—C54120.2 (3)
Co2—C1—Fe187.81 (13)C52—C53—H53119.9
C2—S2—C197.32 (15)C54—C53—H53119.9
C2—S2—F3122.72 (12)C55—C54—C53120.1 (3)
C1—S2—F3136.38 (11)C55—C54—H54120.0
C2—S2—O3159.01 (12)C53—C54—H54120.0
C1—S2—O395.49 (11)C54—C55—C56119.5 (3)
F3—S2—O352.94 (6)C54—C55—H55120.3
C2—S2—S5138.33 (11)C56—C55—H55120.3
C1—S2—S5115.77 (11)C55—C56—C51121.4 (3)
C2—S2—C60130.20 (12)C55—C56—H56119.3
C1—S2—C60132.48 (12)C51—C56—H56119.3
S4—C2—S2120.38 (19)O1—S5—O3115.12 (15)
S4—C2—S3118.30 (18)O1—S5—O2115.05 (14)
S2—C2—S3121.31 (19)O3—S5—O2114.79 (14)
C2—S3—C3104.35 (16)O1—S5—C60103.03 (16)
S3—C3—H3A109.5O3—S5—C60103.68 (15)
S3—C3—H3B109.5O2—S5—C60102.73 (15)
H3A—C3—H3B109.5O1—S5—S2172.58 (11)
S3—C3—H3C109.5O3—S5—S260.23 (10)
H3A—C3—H3C109.5O2—S5—S264.80 (10)
H3B—C3—H3C109.5C60—S5—S284.03 (12)
C2—S4—Fe1106.84 (11)S5—O3—S297.59 (12)
O4—C4—Fe1177.4 (3)F1—C60—F3107.7 (3)
Fe1—C4—O4i165.73 (15)F1—C60—F2107.5 (3)
C4—O4—O4i158.3 (3)F3—C60—F2106.7 (3)
C15—C11—C12107.9 (3)F1—C60—S5110.9 (2)
C15—C11—Co170.08 (19)F3—C60—S5112.1 (2)
C12—C11—Co170.18 (19)F2—C60—S5111.6 (2)
C15—C11—H11126.0F1—C60—S2118.6 (2)
C12—C11—H11126.0F2—C60—S2130.3 (2)
Co1—C11—H11125.3S5—C60—S269.14 (10)
C11—C12—C13107.7 (3)C60—F3—S2119.84 (19)
C11—C12—Co169.55 (19)
Symmetry codes: (i) −x+1, −y+1, −z+2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O20.982.563.477 (4)156
C3—H3C···F30.982.623.297 (4)127
C11—H11···O30.952.413.293 (4)154
C21—H21···O20.952.643.588 (4)174
C21—H21···O30.952.643.235 (4)121
C13—H13···O1ii0.952.423.288 (4)152
C14—H14···F1ii0.952.563.248 (4)129
C35—H35···O1iii0.952.533.283 (4)136
C24—H24···O2iv0.952.493.298 (4)143
Symmetry codes: (ii) x, y, z+1; (iii) x−1, −y+3/2, z+1/2; (iv) x, −y+3/2, z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Co2—S12.1275 (9)Fe1—Co22.6149 (6)
Co1—S12.1564 (9)Co1—C11.867 (3)
Fe1—S12.1836 (9)Co1—Co22.4153 (6)
Fe1—C11.891 (3)Co2—C11.880 (3)
Fe1—Co12.5035 (6)
Co2—S1—Co168.64 (3)Co1—C1—Co280.27 (13)
Co2—S1—Fe174.67 (3)Co1—C1—Fe183.54 (13)
Co1—S1—Fe170.45 (3)Co2—C1—Fe187.81 (13)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3A···O20.982.563.477 (4)156
C3—H3C···F30.982.623.297 (4)127
C11—H11···O30.952.413.293 (4)154
C21—H21···O20.952.643.588 (4)174
C21—H21···O30.952.643.235 (4)121
C13—H13···O1i0.952.423.288 (4)152
C14—H14···F1i0.952.563.248 (4)129
C35—H35···O1ii0.952.533.283 (4)136
C24—H24···O2iii0.952.493.298 (4)143
Symmetry codes: (i) x, y, z+1; (ii) x−1, −y+3/2, z+1/2; (iii) x, −y+3/2, z+1/2.
Acknowledgements top

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
References top

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.