Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803000138/wn6131sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803000138/wn6131Isup2.hkl |
CCDC reference: 204653
Reactions were carried out under an atmosphere of purified nitrogen, using standard Schlenk techniques. To 1 g Fe3(CO)12 suspended in 40 ml toluene was added 2 equiv. of thiophenol. The solution changed from black–green to black–red after stirring for 1 h. Stirring was continued, at 343 K, overnight; the solution was then cooled to room temperature, filtered and evaporated to dryness in vacuo. The residue was extracted with 3 x 10 ml hexane, and the combined extracts were reduced to ca 5 ml in vacuo, yielding a red crystal of (I), at 253 K.
H atoms bonded to C were placed in calculated positions, with C—H distances of 0.93 Å, and treated as riding atoms.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1994); data reduction: XPREP in SHELXTL (Siemens, 1994); program(s) used to solve structure: SHELXTL; program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. Molecular structure of the title compound, with the atom-labeling scheme and probability displacement ellipsoids drawn at the 30% level. |
[Fe4C24H10O12S3] | F(000) = 1608 |
Mr = 809.90 | Dx = 1.754 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 9.0026 (2) Å | Cell parameters from 4211 reflections |
b = 12.9509 (4) Å | θ = 2.2–25.1° |
c = 26.5409 (2) Å | µ = 2.12 mm−1 |
β = 97.612 (1)° | T = 293 K |
V = 3067.18 (12) Å3 | Prism, red |
Z = 4 | 0.50 × 0.38 × 0.36 mm |
Siemens SMART CCD area detector diffractometer | 5418 independent reflections |
Radiation source: fine-focus sealed tube | 4103 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.038 |
ϕ and ω scans | θmax = 25.1°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→10 |
Tmin = 0.698, Tmax = 1.000 | k = −10→15 |
9335 measured reflections | l = −31→17 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0017P)2 + 30.5273P] where P = (Fo2 + 2Fc2)/3 |
5418 reflections | (Δ/σ)max < 0.001 |
388 parameters | Δρmax = 0.52 e Å−3 |
0 restraints | Δρmin = −0.41 e Å−3 |
[Fe4C24H10O12S3] | V = 3067.18 (12) Å3 |
Mr = 809.90 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.0026 (2) Å | µ = 2.12 mm−1 |
b = 12.9509 (4) Å | T = 293 K |
c = 26.5409 (2) Å | 0.50 × 0.38 × 0.36 mm |
β = 97.612 (1)° |
Siemens SMART CCD area detector diffractometer | 5418 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 4103 reflections with I > 2σ(I) |
Tmin = 0.698, Tmax = 1.000 | Rint = 0.038 |
9335 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0017P)2 + 30.5273P] where P = (Fo2 + 2Fc2)/3 |
5418 reflections | Δρmax = 0.52 e Å−3 |
388 parameters | Δρmin = −0.41 e Å−3 |
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. |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.09433 (13) | 0.24175 (9) | 0.23918 (4) | 0.0427 (3) | |
Fe2 | −0.10971 (13) | 0.37690 (9) | 0.23045 (4) | 0.0442 (3) | |
Fe3 | 0.18804 (13) | 0.42252 (9) | 0.12543 (4) | 0.0429 (3) | |
Fe4 | −0.03081 (13) | 0.31485 (10) | 0.08524 (4) | 0.0469 (3) | |
S1 | 0.0292 (2) | 0.33728 (15) | 0.16897 (7) | 0.0397 (4) | |
S2 | 0.1285 (2) | 0.40790 (16) | 0.26679 (7) | 0.0458 (5) | |
S3 | 0.2084 (2) | 0.25558 (16) | 0.09927 (7) | 0.0464 (5) | |
O1 | −0.0556 (10) | 0.0610 (6) | 0.1897 (3) | 0.097 (3) | |
O2 | 0.4086 (8) | 0.1824 (6) | 0.2350 (3) | 0.087 (2) | |
O3 | 0.0586 (8) | 0.1685 (5) | 0.3412 (2) | 0.0714 (19) | |
O4 | −0.2400 (9) | 0.3402 (6) | 0.3241 (3) | 0.092 (2) | |
O5 | −0.3472 (8) | 0.2529 (6) | 0.1733 (3) | 0.089 (2) | |
O6 | −0.2307 (8) | 0.5863 (6) | 0.2104 (3) | 0.086 (2) | |
O7 | 0.0450 (8) | 0.6191 (5) | 0.1437 (3) | 0.079 (2) | |
O8 | 0.3090 (9) | 0.5143 (6) | 0.0386 (3) | 0.099 (3) | |
O9 | 0.4564 (8) | 0.4401 (5) | 0.2017 (3) | 0.078 (2) | |
O10 | −0.2788 (8) | 0.4590 (7) | 0.0881 (3) | 0.090 (2) | |
O11 | −0.1958 (10) | 0.1183 (7) | 0.0711 (3) | 0.109 (3) | |
O12 | −0.0093 (10) | 0.3753 (7) | −0.0196 (3) | 0.100 (3) | |
C1 | 0.0040 (11) | 0.1305 (7) | 0.2090 (3) | 0.059 (2) | |
C2 | 0.2877 (11) | 0.2042 (7) | 0.2362 (3) | 0.054 (2) | |
C3 | 0.0739 (9) | 0.1967 (6) | 0.3017 (3) | 0.048 (2) | |
C4 | −0.1876 (10) | 0.3564 (7) | 0.2886 (3) | 0.058 (2) | |
C5 | −0.2595 (11) | 0.3024 (8) | 0.1962 (3) | 0.059 (2) | |
C6 | −0.1816 (10) | 0.5073 (7) | 0.2172 (3) | 0.052 (2) | |
C7 | 0.1010 (10) | 0.5427 (7) | 0.1367 (3) | 0.051 (2) | |
C8 | 0.2629 (11) | 0.4766 (7) | 0.0717 (3) | 0.062 (2) | |
C9 | 0.3535 (10) | 0.4330 (6) | 0.1714 (4) | 0.051 (2) | |
C10 | −0.1848 (10) | 0.4017 (8) | 0.0861 (3) | 0.058 (2) | |
C11 | −0.1323 (12) | 0.1941 (9) | 0.0770 (4) | 0.073 (3) | |
C12 | −0.0176 (11) | 0.3502 (8) | 0.0207 (4) | 0.065 (3) | |
C13 | 0.1567 (11) | 0.4226 (6) | 0.3344 (3) | 0.056 (2) | |
C14 | 0.2785 (14) | 0.3759 (9) | 0.3613 (4) | 0.088 (4) | |
H14A | 0.3412 | 0.3342 | 0.3448 | 0.105* | |
C15 | 0.3077 (18) | 0.3913 (11) | 0.4136 (5) | 0.113 (5) | |
H15A | 0.3883 | 0.3583 | 0.4325 | 0.136* | |
C16 | 0.220 (2) | 0.4537 (12) | 0.4365 (5) | 0.114 (5) | |
H16A | 0.2414 | 0.4643 | 0.4714 | 0.137* | |
C17 | 0.0994 (18) | 0.5020 (9) | 0.4109 (5) | 0.100 (4) | |
H17A | 0.0395 | 0.5449 | 0.4278 | 0.120* | |
C18 | 0.0666 (12) | 0.4864 (7) | 0.3585 (3) | 0.069 (3) | |
H18A | −0.0154 | 0.5190 | 0.3401 | 0.082* | |
C19 | 0.2912 (10) | 0.2437 (7) | 0.0416 (3) | 0.052 (2) | |
C20 | 0.4306 (11) | 0.2807 (8) | 0.0394 (4) | 0.071 (3) | |
H20A | 0.4822 | 0.3137 | 0.0675 | 0.086* | |
C21 | 0.4975 (14) | 0.2699 (10) | −0.0045 (5) | 0.086 (3) | |
H21A | 0.5923 | 0.2969 | −0.0064 | 0.104* | |
C22 | 0.4211 (16) | 0.2186 (10) | −0.0452 (4) | 0.093 (4) | |
H22A | 0.4644 | 0.2125 | −0.0750 | 0.112* | |
C23 | 0.2810 (15) | 0.1758 (10) | −0.0431 (4) | 0.091 (4) | |
H23A | 0.2311 | 0.1398 | −0.0706 | 0.109* | |
C24 | 0.2179 (11) | 0.1883 (8) | 0.0013 (3) | 0.065 (3) | |
H24A | 0.1249 | 0.1591 | 0.0040 | 0.078* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0523 (7) | 0.0381 (6) | 0.0384 (6) | 0.0025 (5) | 0.0089 (5) | 0.0020 (5) |
Fe2 | 0.0454 (7) | 0.0475 (7) | 0.0409 (6) | 0.0031 (5) | 0.0098 (5) | 0.0005 (5) |
Fe3 | 0.0476 (7) | 0.0424 (6) | 0.0392 (6) | −0.0010 (5) | 0.0070 (5) | 0.0046 (5) |
Fe4 | 0.0489 (7) | 0.0553 (7) | 0.0356 (6) | −0.0014 (6) | 0.0022 (5) | −0.0010 (5) |
S1 | 0.0429 (11) | 0.0442 (11) | 0.0321 (9) | −0.0009 (9) | 0.0053 (8) | 0.0011 (8) |
S2 | 0.0528 (12) | 0.0438 (11) | 0.0400 (10) | 0.0007 (9) | 0.0031 (9) | 0.0003 (9) |
S3 | 0.0533 (12) | 0.0475 (12) | 0.0388 (10) | 0.0030 (10) | 0.0078 (9) | 0.0002 (9) |
O1 | 0.145 (7) | 0.062 (5) | 0.081 (5) | −0.034 (5) | 0.001 (5) | −0.014 (4) |
O2 | 0.066 (5) | 0.100 (6) | 0.098 (6) | 0.026 (4) | 0.026 (4) | 0.022 (5) |
O3 | 0.108 (5) | 0.063 (4) | 0.047 (4) | 0.001 (4) | 0.026 (4) | 0.011 (3) |
O4 | 0.111 (6) | 0.109 (6) | 0.065 (5) | 0.005 (5) | 0.047 (4) | 0.015 (4) |
O5 | 0.068 (5) | 0.111 (6) | 0.090 (5) | −0.033 (4) | 0.015 (4) | −0.027 (5) |
O6 | 0.080 (5) | 0.061 (5) | 0.116 (6) | 0.021 (4) | 0.014 (4) | 0.009 (4) |
O7 | 0.100 (6) | 0.053 (4) | 0.088 (5) | 0.012 (4) | 0.026 (4) | −0.002 (4) |
O8 | 0.122 (7) | 0.094 (6) | 0.092 (6) | 0.009 (5) | 0.051 (5) | 0.046 (5) |
O9 | 0.060 (4) | 0.077 (5) | 0.091 (5) | −0.005 (4) | −0.016 (4) | −0.005 (4) |
O10 | 0.069 (5) | 0.113 (7) | 0.084 (5) | 0.029 (5) | −0.005 (4) | −0.007 (5) |
O11 | 0.125 (7) | 0.094 (6) | 0.103 (6) | −0.040 (6) | −0.007 (5) | −0.008 (5) |
O12 | 0.134 (7) | 0.122 (7) | 0.044 (4) | 0.038 (6) | 0.018 (4) | 0.027 (4) |
C1 | 0.075 (6) | 0.050 (5) | 0.049 (5) | −0.010 (5) | 0.003 (4) | −0.003 (4) |
C2 | 0.069 (6) | 0.051 (5) | 0.044 (5) | 0.002 (5) | 0.014 (4) | 0.008 (4) |
C3 | 0.056 (5) | 0.041 (5) | 0.049 (5) | 0.001 (4) | 0.010 (4) | 0.007 (4) |
C4 | 0.065 (6) | 0.058 (6) | 0.051 (5) | 0.006 (5) | 0.005 (4) | −0.001 (4) |
C5 | 0.056 (6) | 0.072 (6) | 0.053 (5) | 0.001 (5) | 0.019 (4) | −0.004 (5) |
C6 | 0.052 (5) | 0.049 (5) | 0.054 (5) | 0.005 (4) | 0.006 (4) | −0.006 (4) |
C7 | 0.059 (5) | 0.046 (5) | 0.049 (5) | −0.010 (4) | 0.007 (4) | −0.003 (4) |
C8 | 0.082 (7) | 0.054 (6) | 0.050 (5) | −0.001 (5) | 0.014 (5) | 0.005 (4) |
C9 | 0.047 (5) | 0.040 (5) | 0.069 (6) | −0.002 (4) | 0.012 (4) | 0.003 (4) |
C10 | 0.059 (6) | 0.067 (6) | 0.045 (5) | 0.014 (5) | −0.002 (4) | 0.005 (4) |
C11 | 0.082 (7) | 0.078 (7) | 0.057 (6) | −0.014 (6) | 0.001 (5) | −0.010 (5) |
C12 | 0.070 (6) | 0.072 (7) | 0.053 (6) | 0.013 (5) | 0.008 (5) | 0.008 (5) |
C13 | 0.080 (6) | 0.038 (5) | 0.045 (5) | −0.010 (5) | −0.006 (4) | 0.001 (4) |
C14 | 0.116 (10) | 0.081 (8) | 0.058 (6) | −0.001 (7) | −0.020 (6) | −0.004 (6) |
C15 | 0.162 (14) | 0.085 (9) | 0.075 (9) | 0.002 (9) | −0.050 (9) | 0.009 (7) |
C16 | 0.191 (17) | 0.089 (10) | 0.057 (8) | −0.037 (11) | −0.008 (9) | −0.011 (7) |
C17 | 0.162 (14) | 0.065 (8) | 0.075 (8) | −0.022 (8) | 0.024 (8) | −0.021 (6) |
C18 | 0.101 (8) | 0.059 (6) | 0.047 (5) | −0.009 (6) | 0.012 (5) | −0.015 (5) |
C19 | 0.056 (5) | 0.052 (5) | 0.050 (5) | 0.011 (4) | 0.009 (4) | 0.003 (4) |
C20 | 0.068 (6) | 0.081 (7) | 0.068 (6) | −0.003 (6) | 0.019 (5) | −0.006 (5) |
C21 | 0.077 (7) | 0.108 (10) | 0.080 (8) | −0.002 (7) | 0.031 (6) | −0.005 (7) |
C22 | 0.117 (10) | 0.105 (10) | 0.069 (7) | 0.026 (8) | 0.051 (7) | 0.009 (7) |
C23 | 0.123 (10) | 0.101 (9) | 0.050 (6) | 0.019 (8) | 0.018 (6) | −0.019 (6) |
C24 | 0.074 (6) | 0.068 (6) | 0.056 (6) | 0.007 (5) | 0.016 (5) | −0.008 (5) |
Fe1—C3 | 1.791 (8) | O6—C6 | 1.120 (10) |
Fe1—C1 | 1.790 (9) | O7—C7 | 1.136 (10) |
Fe1—C2 | 1.820 (10) | O8—C8 | 1.132 (10) |
Fe1—S1 | 2.249 (2) | O9—C9 | 1.146 (10) |
Fe1—S2 | 2.281 (2) | O10—C10 | 1.132 (10) |
Fe1—Fe2 | 2.5256 (16) | O11—C11 | 1.137 (12) |
Fe2—C4 | 1.796 (10) | O12—C12 | 1.129 (10) |
Fe2—C5 | 1.803 (10) | C13—C18 | 1.374 (13) |
Fe2—C6 | 1.826 (9) | C13—C14 | 1.367 (13) |
Fe2—S1 | 2.243 (2) | C14—C15 | 1.393 (15) |
Fe2—S2 | 2.267 (2) | C14—H14A | 0.9300 |
Fe3—C7 | 1.786 (9) | C15—C16 | 1.335 (19) |
Fe3—C8 | 1.798 (9) | C15—H15A | 0.9300 |
Fe3—C9 | 1.802 (9) | C16—C17 | 1.353 (18) |
Fe3—S1 | 2.244 (2) | C16—H16A | 0.9300 |
Fe3—S3 | 2.286 (2) | C17—C18 | 1.396 (14) |
Fe3—Fe4 | 2.5313 (16) | C17—H17A | 0.9300 |
Fe4—C12 | 1.793 (10) | C18—H18A | 0.9300 |
Fe4—C10 | 1.787 (10) | C19—C20 | 1.352 (12) |
Fe4—C11 | 1.810 (11) | C19—C24 | 1.381 (12) |
Fe4—S1 | 2.235 (2) | C20—C21 | 1.387 (14) |
Fe4—S3 | 2.270 (2) | C20—H20A | 0.9300 |
S2—C13 | 1.790 (8) | C21—C22 | 1.371 (16) |
S3—C19 | 1.795 (8) | C21—H21A | 0.9300 |
O1—C1 | 1.135 (10) | C22—C23 | 1.386 (16) |
O2—C2 | 1.128 (10) | C22—H22A | 0.9300 |
O3—C3 | 1.135 (9) | C23—C24 | 1.383 (13) |
O4—C4 | 1.128 (10) | C23—H23A | 0.9300 |
O5—C5 | 1.130 (10) | C24—H24A | 0.9300 |
C3—Fe1—C1 | 93.2 (4) | Fe4—S1—Fe2 | 131.96 (10) |
C3—Fe1—C2 | 99.7 (4) | Fe4—S1—Fe3 | 68.81 (7) |
C1—Fe1—C2 | 98.4 (4) | Fe2—S1—Fe3 | 135.79 (10) |
C3—Fe1—S1 | 154.1 (3) | Fe4—S1—Fe1 | 138.98 (10) |
C1—Fe1—S1 | 91.1 (3) | Fe2—S1—Fe1 | 68.43 (7) |
C2—Fe1—S1 | 104.9 (3) | Fe3—S1—Fe1 | 125.67 (9) |
C3—Fe1—S2 | 92.1 (3) | C13—S2—Fe2 | 116.5 (3) |
C1—Fe1—S2 | 159.5 (3) | C13—S2—Fe1 | 114.7 (3) |
C2—Fe1—S2 | 100.2 (3) | Fe2—S2—Fe1 | 67.46 (7) |
S1—Fe1—S2 | 75.90 (8) | C19—S3—Fe4 | 112.4 (3) |
C3—Fe1—Fe2 | 98.5 (3) | C19—S3—Fe3 | 113.5 (3) |
C1—Fe1—Fe2 | 103.6 (3) | Fe4—S3—Fe3 | 67.51 (7) |
C2—Fe1—Fe2 | 150.5 (3) | O1—C1—Fe1 | 178.7 (10) |
S1—Fe1—Fe2 | 55.67 (6) | O2—C2—Fe1 | 178.7 (10) |
S2—Fe1—Fe2 | 56.02 (6) | O3—C3—Fe1 | 178.9 (8) |
C4—Fe2—C5 | 90.2 (4) | O4—C4—Fe2 | 177.1 (9) |
C4—Fe2—C6 | 97.7 (4) | O5—C5—Fe2 | 175.9 (9) |
C5—Fe2—C6 | 100.0 (4) | O6—C6—Fe2 | 176.8 (9) |
C4—Fe2—S1 | 155.4 (3) | O7—C7—Fe3 | 179.6 (9) |
C5—Fe2—S1 | 87.8 (3) | O8—C8—Fe3 | 177.4 (9) |
C6—Fe2—S1 | 106.8 (3) | O9—C9—Fe3 | 178.1 (8) |
C4—Fe2—S2 | 96.6 (3) | O10—C10—Fe4 | 177.2 (9) |
C5—Fe2—S2 | 155.7 (3) | O11—C11—Fe4 | 179.1 (10) |
C6—Fe2—S2 | 102.1 (3) | O12—C12—Fe4 | 178.1 (10) |
S1—Fe2—S2 | 76.29 (8) | C18—C13—C14 | 120.4 (9) |
C4—Fe2—Fe1 | 100.4 (3) | C18—C13—S2 | 121.1 (7) |
C5—Fe2—Fe1 | 99.3 (3) | C14—C13—S2 | 118.2 (8) |
C6—Fe2—Fe1 | 153.3 (3) | C13—C14—C15 | 119.2 (12) |
S1—Fe2—Fe1 | 55.90 (6) | C13—C14—H14A | 120.4 |
S2—Fe2—Fe1 | 56.52 (6) | C15—C14—H14A | 120.4 |
C7—Fe3—C8 | 90.8 (4) | C16—C15—C14 | 119.8 (13) |
C7—Fe3—C9 | 99.4 (4) | C16—C15—H15A | 120.1 |
C8—Fe3—C9 | 98.3 (4) | C14—C15—H15A | 120.1 |
C7—Fe3—S1 | 91.0 (3) | C15—C16—C17 | 122.3 (13) |
C8—Fe3—S1 | 158.6 (3) | C15—C16—H16A | 118.9 |
C9—Fe3—S1 | 102.4 (3) | C17—C16—H16A | 118.9 |
C7—Fe3—S3 | 158.4 (3) | C16—C17—C18 | 118.9 (13) |
C8—Fe3—S3 | 94.2 (3) | C16—C17—H17A | 120.5 |
C9—Fe3—S3 | 100.6 (3) | C18—C17—H17A | 120.5 |
S1—Fe3—S3 | 76.90 (8) | C13—C18—C17 | 119.3 (11) |
C7—Fe3—Fe4 | 102.5 (3) | C13—C18—H18A | 120.3 |
C8—Fe3—Fe4 | 103.5 (3) | C17—C18—H18A | 120.3 |
C9—Fe3—Fe4 | 148.7 (3) | C20—C19—C24 | 120.0 (9) |
S1—Fe3—Fe4 | 55.43 (6) | C20—C19—S3 | 120.0 (7) |
S3—Fe3—Fe4 | 55.95 (6) | C24—C19—S3 | 119.7 (7) |
C12—Fe4—C10 | 90.0 (4) | C19—C20—C21 | 120.7 (10) |
C12—Fe4—C11 | 101.6 (5) | C19—C20—H20A | 119.6 |
C10—Fe4—C11 | 99.5 (5) | C21—C20—H20A | 119.6 |
C12—Fe4—S1 | 151.6 (3) | C22—C21—C20 | 118.8 (11) |
C10—Fe4—S1 | 89.5 (3) | C22—C21—H21A | 120.6 |
C11—Fe4—S1 | 106.5 (3) | C20—C21—H21A | 120.6 |
C12—Fe4—S3 | 93.5 (3) | C21—C22—C23 | 121.7 (10) |
C10—Fe4—S3 | 158.6 (3) | C21—C22—H22A | 119.1 |
C11—Fe4—S3 | 100.4 (4) | C23—C22—H22A | 119.1 |
S1—Fe4—S3 | 77.40 (8) | C22—C23—C24 | 117.8 (11) |
C12—Fe4—Fe3 | 96.6 (3) | C22—C23—H23A | 121.1 |
C10—Fe4—Fe3 | 102.1 (3) | C24—C23—H23A | 121.1 |
C11—Fe4—Fe3 | 151.6 (3) | C19—C24—C23 | 120.8 (10) |
S1—Fe4—Fe3 | 55.77 (6) | C19—C24—H24A | 119.6 |
S3—Fe4—Fe3 | 56.54 (6) | C23—C24—H24A | 119.6 |
C3—Fe1—Fe2—C4 | −4.4 (4) | C3—Fe1—S2—C13 | 11.0 (5) |
C1—Fe1—Fe2—C4 | 91.0 (4) | C1—Fe1—S2—C13 | 115.8 (9) |
C2—Fe1—Fe2—C4 | −132.0 (6) | C2—Fe1—S2—C13 | −89.2 (4) |
S1—Fe1—Fe2—C4 | 172.9 (3) | S1—Fe1—S2—C13 | 167.8 (4) |
S2—Fe1—Fe2—C4 | −91.1 (3) | Fe2—Fe1—S2—C13 | 109.9 (4) |
C3—Fe1—Fe2—C5 | −96.3 (4) | C3—Fe1—S2—Fe2 | −98.9 (3) |
C1—Fe1—Fe2—C5 | −0.9 (4) | C1—Fe1—S2—Fe2 | 5.9 (8) |
C2—Fe1—Fe2—C5 | 136.1 (6) | C2—Fe1—S2—Fe2 | 160.8 (3) |
S1—Fe1—Fe2—C5 | 80.9 (3) | S1—Fe1—S2—Fe2 | 57.86 (7) |
S2—Fe1—Fe2—C5 | 177.0 (3) | C12—Fe4—S3—C19 | −11.6 (5) |
C3—Fe1—Fe2—C6 | 127.6 (7) | C10—Fe4—S3—C19 | −110.8 (9) |
C1—Fe1—Fe2—C6 | −137.1 (7) | C11—Fe4—S3—C19 | 90.8 (5) |
C2—Fe1—Fe2—C6 | −0.1 (8) | S1—Fe4—S3—C19 | −164.4 (3) |
S1—Fe1—Fe2—C6 | −55.2 (6) | Fe3—Fe4—S3—C19 | −107.3 (3) |
S2—Fe1—Fe2—C6 | 40.8 (6) | C12—Fe4—S3—Fe3 | 95.6 (3) |
C3—Fe1—Fe2—S1 | −177.3 (3) | C10—Fe4—S3—Fe3 | −3.6 (8) |
C1—Fe1—Fe2—S1 | −81.9 (3) | C11—Fe4—S3—Fe3 | −161.9 (3) |
C2—Fe1—Fe2—S1 | 55.1 (6) | S1—Fe4—S3—Fe3 | −57.09 (7) |
S2—Fe1—Fe2—S1 | 96.01 (9) | C7—Fe3—S3—C19 | 105.2 (8) |
C3—Fe1—Fe2—S2 | 86.7 (3) | C8—Fe3—S3—C19 | 2.2 (4) |
C1—Fe1—Fe2—S2 | −177.9 (3) | C9—Fe3—S3—C19 | −97.1 (4) |
C2—Fe1—Fe2—S2 | −40.9 (6) | S1—Fe3—S3—C19 | 162.6 (3) |
S1—Fe1—Fe2—S2 | −96.01 (9) | Fe4—Fe3—S3—C19 | 105.7 (3) |
C7—Fe3—Fe4—C12 | 90.0 (4) | C7—Fe3—S3—Fe4 | −0.5 (8) |
C8—Fe3—Fe4—C12 | −3.9 (4) | C8—Fe3—S3—Fe4 | −103.4 (3) |
C9—Fe3—Fe4—C12 | −136.8 (6) | C9—Fe3—S3—Fe4 | 157.3 (3) |
S1—Fe3—Fe4—C12 | 172.5 (3) | S1—Fe3—S3—Fe4 | 56.91 (7) |
S3—Fe3—Fe4—C12 | −89.9 (3) | C3—Fe1—C1—O1 | 101 (40) |
C7—Fe3—Fe4—C10 | −1.5 (4) | C2—Fe1—C1—O1 | −159 (100) |
C8—Fe3—Fe4—C10 | −95.4 (4) | S1—Fe1—C1—O1 | −54 (40) |
C9—Fe3—Fe4—C10 | 131.7 (6) | S2—Fe1—C1—O1 | −4 (41) |
S1—Fe3—Fe4—C10 | 81.0 (3) | Fe2—Fe1—C1—O1 | 1 (40) |
S3—Fe3—Fe4—C10 | 178.7 (3) | C3—Fe1—C2—O2 | −77 (41) |
C7—Fe3—Fe4—C11 | −140.2 (8) | C1—Fe1—C2—O2 | −172 (100) |
C8—Fe3—Fe4—C11 | 125.9 (8) | S1—Fe1—C2—O2 | 95 (41) |
C9—Fe3—Fe4—C11 | −7.0 (9) | S2—Fe1—C2—O2 | 17 (41) |
S1—Fe3—Fe4—C11 | −57.7 (7) | Fe2—Fe1—C2—O2 | 50 (41) |
S3—Fe3—Fe4—C11 | 40.0 (7) | C1—Fe1—C3—O3 | −74 (41) |
C7—Fe3—Fe4—S1 | −82.5 (3) | C2—Fe1—C3—O3 | −173 (100) |
C8—Fe3—Fe4—S1 | −176.4 (3) | S1—Fe1—C3—O3 | 25 (42) |
C9—Fe3—Fe4—S1 | 50.7 (5) | S2—Fe1—C3—O3 | 86 (41) |
S3—Fe3—Fe4—S1 | 97.67 (9) | Fe2—Fe1—C3—O3 | 30 (41) |
C7—Fe3—Fe4—S3 | 179.8 (3) | C5—Fe2—C4—O4 | 17 (18) |
C8—Fe3—Fe4—S3 | 86.0 (3) | C6—Fe2—C4—O4 | 117 (18) |
C9—Fe3—Fe4—S3 | −46.9 (5) | S1—Fe2—C4—O4 | −69 (18) |
S1—Fe3—Fe4—S3 | −97.67 (9) | S2—Fe2—C4—O4 | −140 (18) |
C12—Fe4—S1—Fe2 | 117.4 (7) | Fe1—Fe2—C4—O4 | −83 (18) |
C10—Fe4—S1—Fe2 | 28.2 (3) | C4—Fe2—C5—O5 | −135 (14) |
C11—Fe4—S1—Fe2 | −71.6 (4) | C6—Fe2—C5—O5 | 128 (14) |
S3—Fe4—S1—Fe2 | −168.84 (14) | S1—Fe2—C5—O5 | 21 (14) |
Fe3—Fe4—S1—Fe2 | 133.25 (15) | S2—Fe2—C5—O5 | −28 (14) |
C12—Fe4—S1—Fe3 | −15.8 (7) | Fe1—Fe2—C5—O5 | −34 (14) |
C10—Fe4—S1—Fe3 | −105.0 (3) | C4—Fe2—C6—O6 | −21 (16) |
C11—Fe4—S1—Fe3 | 155.2 (4) | C5—Fe2—C6—O6 | 70 (16) |
S3—Fe4—S1—Fe3 | 57.91 (7) | S1—Fe2—C6—O6 | 161 (16) |
C12—Fe4—S1—Fe1 | −136.3 (7) | S2—Fe2—C6—O6 | −120 (16) |
C10—Fe4—S1—Fe1 | 134.5 (3) | Fe1—Fe2—C6—O6 | −154 (16) |
C11—Fe4—S1—Fe1 | 34.7 (4) | C8—Fe3—C7—O7 | 66 (100) |
S3—Fe4—S1—Fe1 | −62.57 (15) | C9—Fe3—C7—O7 | 165 (100) |
Fe3—Fe4—S1—Fe1 | −120.47 (16) | S1—Fe3—C7—O7 | −93 (100) |
C4—Fe2—S1—Fe4 | 120.3 (7) | S3—Fe3—C7—O7 | −38 (100) |
C5—Fe2—S1—Fe4 | 34.6 (3) | Fe4—Fe3—C7—O7 | −38 (100) |
C6—Fe2—S1—Fe4 | −65.3 (3) | C7—Fe3—C8—O8 | 16 (21) |
S2—Fe2—S1—Fe4 | −164.02 (14) | C9—Fe3—C8—O8 | −83 (21) |
Fe1—Fe2—S1—Fe4 | 137.35 (15) | S1—Fe3—C8—O8 | 111 (21) |
C4—Fe2—S1—Fe3 | −136.6 (7) | S3—Fe3—C8—O8 | 175 (21) |
C5—Fe2—S1—Fe3 | 137.7 (3) | Fe4—Fe3—C8—O8 | 119 (21) |
C6—Fe2—S1—Fe3 | 37.8 (3) | C7—Fe3—C9—O9 | 54 (25) |
S2—Fe2—S1—Fe3 | −60.89 (14) | C8—Fe3—C9—O9 | 147 (25) |
Fe1—Fe2—S1—Fe3 | −119.52 (15) | S1—Fe3—C9—O9 | −39 (25) |
C4—Fe2—S1—Fe1 | −17.1 (7) | S3—Fe3—C9—O9 | −118 (25) |
C5—Fe2—S1—Fe1 | −102.8 (3) | Fe4—Fe3—C9—O9 | −80 (25) |
C6—Fe2—S1—Fe1 | 157.4 (3) | C12—Fe4—C10—O10 | −116 (20) |
S2—Fe2—S1—Fe1 | 58.63 (7) | C11—Fe4—C10—O10 | 143 (19) |
C7—Fe3—S1—Fe4 | 104.5 (3) | S1—Fe4—C10—O10 | 36 (20) |
C8—Fe3—S1—Fe4 | 9.8 (9) | S3—Fe4—C10—O10 | −16 (20) |
C9—Fe3—S1—Fe4 | −155.7 (3) | Fe3—Fe4—C10—O10 | −19 (20) |
S3—Fe3—S1—Fe4 | −57.47 (7) | C12—Fe4—C11—O11 | 10 (69) |
C7—Fe3—S1—Fe2 | −24.5 (3) | C10—Fe4—C11—O11 | 102 (69) |
C8—Fe3—S1—Fe2 | −119.3 (9) | S1—Fe4—C11—O11 | −166 (69) |
C9—Fe3—S1—Fe2 | 75.3 (3) | S3—Fe4—C11—O11 | −86 (69) |
S3—Fe3—S1—Fe2 | 173.49 (14) | Fe3—Fe4—C11—O11 | −119 (69) |
Fe4—Fe3—S1—Fe2 | −129.04 (15) | C10—Fe4—C12—O12 | 51 (27) |
C7—Fe3—S1—Fe1 | −119.6 (3) | C11—Fe4—C12—O12 | 151 (27) |
C8—Fe3—S1—Fe1 | 145.6 (9) | S1—Fe4—C12—O12 | −38 (27) |
C9—Fe3—S1—Fe1 | −19.8 (3) | S3—Fe4—C12—O12 | −108 (27) |
S3—Fe3—S1—Fe1 | 78.40 (12) | Fe3—Fe4—C12—O12 | −51 (27) |
Fe4—Fe3—S1—Fe1 | 135.87 (13) | Fe2—S2—C13—C18 | −48.4 (8) |
C3—Fe1—S1—Fe4 | −123.7 (6) | Fe1—S2—C13—C18 | −124.3 (7) |
C1—Fe1—S1—Fe4 | −24.1 (3) | Fe2—S2—C13—C14 | 137.4 (7) |
C2—Fe1—S1—Fe4 | 74.9 (3) | Fe1—S2—C13—C14 | 61.4 (9) |
S2—Fe1—S1—Fe4 | 171.89 (16) | C18—C13—C14—C15 | 1.9 (17) |
Fe2—Fe1—S1—Fe4 | −129.87 (16) | S2—C13—C14—C15 | 176.2 (9) |
C3—Fe1—S1—Fe2 | 6.2 (6) | C13—C14—C15—C16 | −2 (2) |
C1—Fe1—S1—Fe2 | 105.8 (3) | C14—C15—C16—C17 | 1 (2) |
C2—Fe1—S1—Fe2 | −155.3 (3) | C15—C16—C17—C18 | 0 (2) |
S2—Fe1—S1—Fe2 | −58.24 (7) | C14—C13—C18—C17 | −0.9 (15) |
C3—Fe1—S1—Fe3 | 137.9 (6) | S2—C13—C18—C17 | −175.1 (8) |
C1—Fe1—S1—Fe3 | −122.6 (3) | C16—C17—C18—C13 | 0.1 (17) |
C2—Fe1—S1—Fe3 | −23.6 (3) | Fe4—S3—C19—C20 | 133.2 (7) |
S2—Fe1—S1—Fe3 | 73.44 (12) | Fe3—S3—C19—C20 | 58.9 (8) |
Fe2—Fe1—S1—Fe3 | 131.68 (13) | Fe4—S3—C19—C24 | −52.7 (8) |
C4—Fe2—S2—C13 | −9.3 (4) | Fe3—S3—C19—C24 | −127.0 (7) |
C5—Fe2—S2—C13 | −114.7 (8) | C24—C19—C20—C21 | 4.4 (16) |
C6—Fe2—S2—C13 | 90.1 (4) | S3—C19—C20—C21 | 178.5 (8) |
S1—Fe2—S2—C13 | −165.3 (3) | C19—C20—C21—C22 | −1.6 (18) |
Fe1—Fe2—S2—C13 | −107.4 (3) | C20—C21—C22—C23 | −1.4 (19) |
C4—Fe2—S2—Fe1 | 98.1 (3) | C21—C22—C23—C24 | 1.5 (19) |
C5—Fe2—S2—Fe1 | −7.3 (7) | C20—C19—C24—C23 | −4.3 (15) |
C6—Fe2—S2—Fe1 | −162.5 (3) | S3—C19—C24—C23 | −178.4 (8) |
S1—Fe2—S2—Fe1 | −57.96 (7) | C22—C23—C24—C19 | 1.3 (17) |
Experimental details
Crystal data | |
Chemical formula | [Fe4C24H10O12S3] |
Mr | 809.90 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.0026 (2), 12.9509 (4), 26.5409 (2) |
β (°) | 97.612 (1) |
V (Å3) | 3067.18 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.12 |
Crystal size (mm) | 0.50 × 0.38 × 0.36 |
Data collection | |
Diffractometer | Siemens SMART CCD area detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.698, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9335, 5418, 4103 |
Rint | 0.038 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.147, 1.03 |
No. of reflections | 5418 |
No. of parameters | 388 |
H-atom treatment | H-atom parameters constrained |
w = 1/[σ2(Fo2) + (0.0017P)2 + 30.5273P] where P = (Fo2 + 2Fc2)/3 | |
Δρmax, Δρmin (e Å−3) | 0.52, −0.41 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1994), XPREP in SHELXTL (Siemens, 1994), SHELXTL.
Fe1—C3 | 1.791 (8) | Fe3—C7 | 1.786 (9) |
Fe1—C1 | 1.790 (9) | Fe3—C8 | 1.798 (9) |
Fe1—C2 | 1.820 (10) | Fe3—C9 | 1.802 (9) |
Fe1—S1 | 2.249 (2) | Fe3—S1 | 2.244 (2) |
Fe1—S2 | 2.281 (2) | Fe3—S3 | 2.286 (2) |
Fe1—Fe2 | 2.5256 (16) | Fe3—Fe4 | 2.5313 (16) |
Fe2—C4 | 1.796 (10) | Fe4—C12 | 1.793 (10) |
Fe2—C5 | 1.803 (10) | Fe4—C10 | 1.787 (10) |
Fe2—C6 | 1.826 (9) | Fe4—C11 | 1.810 (11) |
Fe2—S1 | 2.243 (2) | Fe4—S1 | 2.235 (2) |
Fe2—S2 | 2.267 (2) | Fe4—S3 | 2.270 (2) |
Fe4—S1—Fe2 | 131.96 (10) | Fe2—S1—Fe1 | 68.43 (7) |
Fe4—S1—Fe3 | 68.81 (7) | Fe3—S1—Fe1 | 125.67 (9) |
Fe2—S1—Fe3 | 135.79 (10) | Fe2—S2—Fe1 | 67.46 (7) |
Fe4—S1—Fe1 | 138.98 (10) | Fe4—S3—Fe3 | 67.51 (7) |
Hydrogenases are utilized by numerous microorganisms to process hydrogen, both in the production and uptake of molecular hydrogen, in support of their metabolism. Fairly recently, crystallographic investigations of the so-called Fe-only hydrogenases discovered a six-iron H-cluster containing an Fe2(µ-SR)2(CN)2(CO)3Ln core [R is alkyl, L is H2O], and a thiolate-linked Fe4S4(SR)4 cluster. The metabolism of hydrogen is facilitated at a novel 2Fe2S center in Fe-only hydrogenase (Peters et al., 1998, Nicolet et al., 1999, Nicolet et al., 2001). To simulate the organometallic structure Fe2(SR)2(CN)2(CO)4 of the H-cluster, we repeated the preparation of Fe2(SR)2(CO)6 by the reaction of Fe3(CO)12 with thiophenol, using the method of Rauchfuss (Gloaguen et al., 2001). We obtained the title compound, (I), which represents a new example of an Fe4S3 core cluster containing a bridging thiophenyl ligand. However, similar structures have been reported in other complexes, viz. [CH3SFe2(CO)6]2S (Coleman et al., 1967), [C6H9SFe2(CO)6]2S (Kolobkov et al., 1986), and [EtSFe2(CO)6]2S (Song et al., 1988).
Complex (I) contains two Fe2S(CO)6 subclusters Fe1,S2,Fe2 and Fe3,S3,Fe4, connected through the inorganic sulfur atom, µ4-S1, as shown in Fig. 1. Each subcluster has a phenyl group, attached to µ2-S2 and µ2-S3, respectively. In each subcluster, two Fe atoms are bridged by the thiophenyl S, with an average Fe—S—Fe angle of 67.48 (7)° and an average Fe—S distance of 2.276 (2) Å. The Fe—Fe separations of 2.526 (16) and 2.532 (16) Å are comparable to those in the H-cluster. The central sulfur atom, S1, connects the two Fe2S(CO)6 fragments, with a shorter Fe—S distance, averaging 2.243 (2) Å. The Fe—S1—Fe angles, ranging from 68.44 (7)° to 138.97 (10)°, show that the Fe4S tetrahedron is very distorted. In addition to the coordination of one thiophenyl S and one µ4-S, the 18-electron shell of each Fe atom is completed by three terminal carbonyl groups, with an average Fe—C bond length of 1.800 (10) Å.