Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803001545/dn6053sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803001545/dn6053Isup2.hkl |
CCDC reference: 204663
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.038
- wR factor = 0.055
- Data-to-parameter ratio = 13.9
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Le complexe tétranucléaire (Fe4S3C36O11PH19) est préparé sous activation thermique du TN, où un carbonyle est substitué par le ligand triphenylphosphine, 6,64 × 10−4 moles de TN et 1,2 × 10−3 moles de PPh3 sont dissouts dans l'acétone et chauffés á 328 K pendant 8 h sous azote et à l'abri de la lumière. Le solvant est distillé et le résidu est séparé par chromatographie préparative sur plaque (éluant: éther de pétrole/éther éthylique 9:1). Le complexe monosubstitué (Fe4S3C36O11PH19) est récupéré aprés lavage du gel de silice à l'acétone puis recristallisé dans un mélange éther /hexane 1:1, on obtient des cristaux rouges prismatiques.
Data collection: KappaCCD Reference Manual (Nonius, 1998); cell refinement: DENZO and SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK; program(s) used to solve structure: SIR97 (Altomare et al., 1998); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
[Fe4C7H4S3)(C18H15P)(CO)11] | F(000) = 1960 |
Mr = 978.09 | Dx = 1.644 Mg m−3 |
Monoclinic, P21/n | Melting point: 210 K |
Hall symbol: -P 2yn | Mo Kα radiation, λ = 0.71073 Å |
a = 9.725 (5) Å | Cell parameters from 28122 reflections |
b = 17.954 (5) Å | θ = 5.8–25.0° |
c = 22.885 (5) Å | µ = 1.70 mm−1 |
β = 98.488 (5)° | T = 293 K |
V = 3952 (2) Å3 | Prism, red |
Z = 4 | 0.3 × 0.2 × 0.1 mm |
Nonius KappaCCD diffractometer | 6888 independent reflections |
Radiation source: fine-focus sealed tube | 3440 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.090 |
ϕ scans | θmax = 25.0°, θmin = 5.8° |
Absorption correction: part of the refinement model (ΔF) (Walker et al., 1983) | h = −11→11 |
Tmin = 0.618, Tmax = 0.887 | k = −21→20 |
28122 measured reflections | l = −27→27 |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 0.80 | w = 1/[σ2(Fo2) + (0.0114P)2] where P = (Fo2 + 2Fc2)/3 |
6888 reflections | (Δ/σ)max = 0.001 |
496 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
[Fe4C7H4S3)(C18H15P)(CO)11] | V = 3952 (2) Å3 |
Mr = 978.09 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.725 (5) Å | µ = 1.70 mm−1 |
b = 17.954 (5) Å | T = 293 K |
c = 22.885 (5) Å | 0.3 × 0.2 × 0.1 mm |
β = 98.488 (5)° |
Nonius KappaCCD diffractometer | 6888 independent reflections |
Absorption correction: part of the refinement model (ΔF) (Walker et al., 1983) | 3440 reflections with I > 2σ(I) |
Tmin = 0.618, Tmax = 0.887 | Rint = 0.090 |
28122 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.055 | H-atom parameters constrained |
S = 0.80 | Δρmax = 0.27 e Å−3 |
6888 reflections | Δρmin = −0.34 e Å−3 |
496 parameters |
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 | ||
Fe4 | 0.90139 (5) | 0.17834 (3) | 0.248179 (18) | 0.03719 (15) | |
Fe1 | 0.62253 (6) | 0.15000 (3) | 0.37526 (2) | 0.05023 (17) | |
Fe2 | 0.87380 (6) | 0.12435 (3) | 0.41937 (2) | 0.05073 (17) | |
Fe3 | 0.75163 (5) | 0.30460 (3) | 0.244372 (19) | 0.04130 (15) | |
S2 | 0.80901 (9) | 0.18365 (5) | 0.33473 (3) | 0.0394 (2) | |
S3 | 0.96675 (9) | 0.29290 (5) | 0.28665 (4) | 0.0420 (3) | |
P | 0.98556 (9) | 0.18803 (5) | 0.16136 (4) | 0.0394 (3) | |
S1 | 0.73890 (10) | 0.21262 (6) | 0.45284 (4) | 0.0524 (3) | |
C1 | 0.8318 (3) | 0.28204 (18) | 0.33123 (13) | 0.0358 (9) | |
C25 | 1.1060 (4) | 0.1121 (2) | 0.15215 (13) | 0.0429 (10) | |
C16 | 0.6090 (4) | 0.2424 (2) | 0.22538 (14) | 0.0474 (11) | |
C15 | 0.6536 (4) | 0.3828 (2) | 0.26191 (15) | 0.0475 (11) | |
C31 | 1.0831 (3) | 0.2724 (2) | 0.15365 (15) | 0.0411 (10) | |
O17 | 1.1486 (3) | 0.09584 (16) | 0.30067 (11) | 0.0790 (10) | |
C3 | 0.7797 (3) | 0.30588 (19) | 0.43480 (15) | 0.0409 (9) | |
C17 | 1.0519 (4) | 0.1268 (2) | 0.27916 (14) | 0.0501 (11) | |
C2 | 0.8220 (3) | 0.3306 (2) | 0.38203 (15) | 0.0403 (9) | |
O18 | 0.7113 (3) | 0.06126 (15) | 0.19742 (11) | 0.0653 (8) | |
O16 | 0.5136 (3) | 0.20565 (15) | 0.21135 (11) | 0.0709 (9) | |
C18 | 0.7877 (4) | 0.1071 (2) | 0.21690 (15) | 0.0434 (10) | |
C14 | 0.7616 (4) | 0.3405 (2) | 0.17219 (18) | 0.0606 (12) | |
C29 | 1.1428 (7) | −0.0204 (3) | 0.14401 (19) | 0.0876 (15) | |
H29 | 1.1075 | −0.0687 | 0.1421 | 0.105* | |
C36 | 1.0556 (4) | 0.3212 (2) | 0.10631 (16) | 0.0576 (11) | |
H36 | 0.9867 | 0.3093 | 0.0750 | 0.069* | |
C32 | 1.1873 (4) | 0.2925 (2) | 0.19956 (15) | 0.0513 (11) | |
H32 | 1.2085 | 0.2610 | 0.2319 | 0.062* | |
O14 | 0.7620 (3) | 0.36722 (17) | 0.12699 (12) | 0.0947 (11) | |
C9 | 0.4918 (4) | 0.2180 (3) | 0.34995 (17) | 0.0628 (13) | |
C19 | 0.8650 (4) | 0.1785 (2) | 0.09213 (15) | 0.0463 (10) | |
O15 | 0.5844 (3) | 0.43111 (17) | 0.27232 (11) | 0.0740 (9) | |
C11 | 0.8569 (5) | 0.0688 (3) | 0.48308 (19) | 0.0805 (15) | |
C7 | 0.8549 (3) | 0.4060 (2) | 0.37819 (15) | 0.0470 (10) | |
H7 | 0.8841 | 0.4233 | 0.3437 | 0.056* | |
C12 | 0.9075 (4) | 0.0434 (3) | 0.37975 (17) | 0.0585 (12) | |
O8 | 0.5403 (3) | 0.0287 (2) | 0.29125 (14) | 0.1073 (13) | |
C26 | 1.2441 (5) | 0.1223 (3) | 0.15142 (15) | 0.0647 (12) | |
H26 | 1.2808 | 0.1702 | 0.1533 | 0.078* | |
O12 | 0.9285 (3) | −0.00926 (17) | 0.35405 (13) | 0.0847 (10) | |
C33 | 1.2592 (4) | 0.3585 (3) | 0.1977 (2) | 0.0699 (13) | |
H33 | 1.3288 | 0.3712 | 0.2285 | 0.084* | |
O9 | 0.4092 (3) | 0.2624 (2) | 0.33605 (13) | 0.0945 (11) | |
C20 | 0.9145 (4) | 0.1604 (2) | 0.04107 (18) | 0.0813 (15) | |
H20 | 1.0098 | 0.1550 | 0.0416 | 0.098* | |
C5 | 0.8018 (4) | 0.4302 (3) | 0.47450 (18) | 0.0669 (13) | |
H5 | 0.7931 | 0.4632 | 0.5051 | 0.080* | |
C6 | 0.8462 (4) | 0.4557 (2) | 0.42323 (19) | 0.0578 (11) | |
H6 | 0.8696 | 0.5055 | 0.4194 | 0.069* | |
C30 | 1.0549 (5) | 0.0402 (3) | 0.14719 (16) | 0.0717 (13) | |
H30 | 0.9600 | 0.0321 | 0.1460 | 0.086* | |
C4 | 0.7708 (4) | 0.3567 (3) | 0.48015 (15) | 0.0572 (12) | |
H4 | 0.7431 | 0.3401 | 0.5151 | 0.069* | |
C8 | 0.5743 (4) | 0.0767 (3) | 0.32267 (19) | 0.0677 (13) | |
C21 | 0.8255 (6) | 0.1500 (3) | −0.01166 (19) | 0.109 (2) | |
H21 | 0.8608 | 0.1376 | −0.0460 | 0.130* | |
C28 | 1.2810 (7) | −0.0084 (4) | 0.14379 (19) | 0.0890 (17) | |
H28 | 1.3403 | −0.0484 | 0.1408 | 0.107* | |
C34 | 1.2276 (5) | 0.4054 (3) | 0.1502 (3) | 0.0860 (15) | |
H34 | 1.2751 | 0.4502 | 0.1492 | 0.103* | |
C27 | 1.3313 (5) | 0.0614 (4) | 0.14790 (18) | 0.0869 (17) | |
H27 | 1.4260 | 0.0691 | 0.1484 | 0.104* | |
C24 | 0.7246 (4) | 0.1868 (2) | 0.08941 (16) | 0.0585 (12) | |
H24 | 0.6882 | 0.1994 | 0.1235 | 0.070* | |
C23 | 0.6354 (5) | 0.1770 (2) | 0.0371 (2) | 0.0793 (14) | |
H23 | 0.5402 | 0.1834 | 0.0362 | 0.095* | |
C35 | 1.1276 (5) | 0.3867 (3) | 0.1047 (2) | 0.0794 (14) | |
H35 | 1.1079 | 0.4184 | 0.0723 | 0.095* | |
C22 | 0.6857 (7) | 0.1582 (3) | −0.0125 (2) | 0.0906 (18) | |
H22 | 0.6251 | 0.1507 | −0.0474 | 0.109* | |
O11 | 0.8466 (4) | 0.0314 (2) | 0.52244 (14) | 0.1293 (15) | |
O10 | 0.4696 (4) | 0.07306 (19) | 0.45847 (14) | 0.1048 (12) | |
O13 | 1.1658 (4) | 0.1685 (2) | 0.44833 (16) | 0.1305 (15) | |
C10 | 0.5300 (5) | 0.1039 (3) | 0.42688 (17) | 0.0691 (14) | |
C13 | 1.0517 (5) | 0.1533 (2) | 0.43836 (17) | 0.0714 (14) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe4 | 0.0357 (3) | 0.0350 (3) | 0.0406 (3) | 0.0017 (3) | 0.0044 (2) | −0.0004 (2) |
Fe1 | 0.0482 (4) | 0.0498 (4) | 0.0536 (3) | −0.0023 (3) | 0.0103 (3) | 0.0094 (3) |
Fe2 | 0.0560 (4) | 0.0505 (4) | 0.0449 (3) | 0.0113 (3) | 0.0051 (3) | 0.0070 (3) |
Fe3 | 0.0411 (3) | 0.0373 (4) | 0.0451 (3) | 0.0040 (3) | 0.0051 (2) | 0.0024 (3) |
S2 | 0.0396 (6) | 0.0370 (6) | 0.0413 (5) | 0.0021 (5) | 0.0050 (4) | 0.0028 (5) |
S3 | 0.0370 (6) | 0.0398 (7) | 0.0496 (6) | −0.0028 (5) | 0.0080 (4) | −0.0036 (5) |
P | 0.0344 (6) | 0.0422 (7) | 0.0406 (5) | −0.0017 (5) | 0.0024 (4) | −0.0032 (5) |
S1 | 0.0559 (7) | 0.0580 (8) | 0.0445 (6) | 0.0079 (6) | 0.0117 (5) | 0.0039 (5) |
C1 | 0.036 (2) | 0.032 (2) | 0.040 (2) | 0.0001 (18) | 0.0069 (16) | 0.0012 (17) |
C25 | 0.039 (3) | 0.046 (3) | 0.045 (2) | 0.001 (2) | 0.0091 (18) | −0.0085 (19) |
C16 | 0.054 (3) | 0.044 (3) | 0.043 (2) | 0.010 (2) | 0.003 (2) | −0.0033 (19) |
C15 | 0.045 (3) | 0.043 (3) | 0.053 (2) | −0.002 (2) | 0.0005 (19) | −0.004 (2) |
C31 | 0.035 (2) | 0.047 (3) | 0.042 (2) | −0.006 (2) | 0.0060 (18) | 0.0006 (19) |
O17 | 0.068 (2) | 0.094 (3) | 0.074 (2) | 0.0378 (19) | 0.0060 (16) | 0.0192 (17) |
C3 | 0.042 (2) | 0.037 (3) | 0.043 (2) | 0.007 (2) | 0.0054 (18) | −0.007 (2) |
C17 | 0.050 (3) | 0.056 (3) | 0.045 (2) | 0.006 (2) | 0.009 (2) | 0.009 (2) |
C2 | 0.031 (2) | 0.043 (3) | 0.046 (2) | 0.004 (2) | 0.0022 (18) | −0.008 (2) |
O18 | 0.061 (2) | 0.054 (2) | 0.0802 (19) | −0.0143 (16) | 0.0093 (15) | −0.0144 (15) |
O16 | 0.049 (2) | 0.064 (2) | 0.093 (2) | −0.0086 (17) | −0.0093 (16) | −0.0143 (16) |
C18 | 0.042 (3) | 0.039 (3) | 0.051 (2) | 0.006 (2) | 0.0108 (19) | −0.001 (2) |
C14 | 0.064 (3) | 0.054 (3) | 0.067 (3) | 0.021 (2) | 0.021 (2) | 0.014 (2) |
C29 | 0.115 (5) | 0.045 (4) | 0.116 (4) | 0.013 (4) | 0.062 (4) | −0.004 (3) |
C36 | 0.065 (3) | 0.052 (3) | 0.056 (3) | −0.013 (3) | 0.008 (2) | 0.006 (2) |
C32 | 0.044 (3) | 0.052 (3) | 0.059 (3) | −0.009 (2) | 0.011 (2) | −0.007 (2) |
O14 | 0.124 (3) | 0.098 (3) | 0.070 (2) | 0.049 (2) | 0.0397 (19) | 0.0398 (19) |
C9 | 0.051 (3) | 0.068 (4) | 0.069 (3) | −0.001 (3) | 0.008 (2) | 0.011 (2) |
C19 | 0.047 (3) | 0.049 (3) | 0.040 (2) | 0.001 (2) | −0.001 (2) | −0.0077 (19) |
O15 | 0.068 (2) | 0.063 (2) | 0.090 (2) | 0.0192 (18) | 0.0064 (16) | −0.0214 (17) |
C11 | 0.091 (4) | 0.092 (4) | 0.066 (3) | 0.049 (3) | 0.034 (3) | 0.031 (3) |
C7 | 0.045 (3) | 0.047 (3) | 0.048 (2) | −0.003 (2) | 0.0033 (19) | −0.007 (2) |
C12 | 0.063 (3) | 0.048 (3) | 0.063 (3) | 0.003 (3) | 0.006 (2) | 0.011 (2) |
O8 | 0.128 (3) | 0.099 (3) | 0.098 (3) | −0.057 (2) | 0.030 (2) | −0.026 (2) |
C26 | 0.049 (3) | 0.064 (3) | 0.079 (3) | 0.004 (3) | 0.001 (2) | −0.029 (2) |
O12 | 0.107 (3) | 0.052 (2) | 0.096 (2) | 0.000 (2) | 0.0200 (18) | −0.0054 (18) |
C33 | 0.059 (3) | 0.082 (4) | 0.071 (3) | −0.028 (3) | 0.014 (2) | −0.019 (3) |
O9 | 0.074 (2) | 0.114 (3) | 0.094 (2) | 0.035 (2) | 0.0081 (18) | 0.0229 (19) |
C20 | 0.057 (3) | 0.133 (5) | 0.053 (3) | 0.009 (3) | 0.001 (2) | −0.021 (3) |
C5 | 0.082 (4) | 0.060 (4) | 0.057 (3) | 0.010 (3) | 0.005 (2) | −0.021 (3) |
C6 | 0.066 (3) | 0.038 (3) | 0.066 (3) | 0.003 (2) | −0.001 (2) | −0.011 (2) |
C30 | 0.070 (3) | 0.054 (4) | 0.101 (3) | 0.005 (3) | 0.047 (3) | −0.001 (3) |
C4 | 0.057 (3) | 0.070 (4) | 0.044 (2) | 0.007 (3) | 0.008 (2) | −0.010 (2) |
C8 | 0.066 (3) | 0.068 (4) | 0.070 (3) | −0.020 (3) | 0.014 (2) | 0.010 (3) |
C21 | 0.101 (5) | 0.166 (6) | 0.052 (3) | 0.021 (4) | −0.013 (3) | −0.036 (3) |
C28 | 0.088 (5) | 0.088 (5) | 0.092 (3) | 0.041 (4) | 0.017 (3) | −0.022 (3) |
C34 | 0.086 (4) | 0.061 (4) | 0.117 (5) | −0.040 (3) | 0.034 (3) | −0.009 (3) |
C27 | 0.052 (3) | 0.103 (5) | 0.101 (4) | 0.017 (4) | −0.007 (3) | −0.043 (4) |
C24 | 0.052 (3) | 0.065 (3) | 0.055 (3) | 0.005 (2) | −0.007 (2) | 0.004 (2) |
C23 | 0.065 (3) | 0.089 (4) | 0.074 (3) | 0.004 (3) | −0.023 (3) | 0.001 (3) |
C35 | 0.091 (4) | 0.063 (4) | 0.087 (4) | −0.012 (3) | 0.022 (3) | 0.021 (3) |
C22 | 0.104 (5) | 0.092 (4) | 0.061 (4) | 0.002 (3) | −0.036 (3) | −0.014 (3) |
O11 | 0.177 (4) | 0.135 (3) | 0.090 (2) | 0.081 (3) | 0.065 (2) | 0.066 (2) |
O10 | 0.113 (3) | 0.109 (3) | 0.102 (2) | −0.028 (2) | 0.046 (2) | 0.030 (2) |
O13 | 0.060 (3) | 0.125 (3) | 0.195 (4) | 0.001 (2) | −0.019 (3) | −0.055 (3) |
C10 | 0.071 (4) | 0.077 (4) | 0.064 (3) | −0.003 (3) | 0.022 (2) | 0.015 (3) |
C13 | 0.062 (4) | 0.070 (4) | 0.077 (3) | 0.013 (3) | −0.007 (3) | −0.016 (2) |
Fe4—C18 | 1.771 (4) | C15—O15 | 1.144 (4) |
Fe4—C17 | 1.787 (4) | C31—C36 | 1.389 (4) |
Fe4—P | 2.2645 (11) | C31—C32 | 1.395 (4) |
Fe4—S3 | 2.2901 (11) | O17—C17 | 1.140 (4) |
Fe4—S2 | 2.2946 (11) | C3—C4 | 1.394 (4) |
Fe4—Fe3 | 2.6890 (10) | C3—C2 | 1.404 (4) |
Fe1—C10 | 1.790 (5) | C2—C7 | 1.396 (4) |
Fe1—C9 | 1.795 (5) | O18—C18 | 1.154 (4) |
Fe1—C8 | 1.798 (5) | C14—O14 | 1.141 (3) |
Fe1—S2 | 2.2385 (13) | C29—C28 | 1.362 (6) |
Fe1—S1 | 2.2592 (11) | C29—C30 | 1.393 (5) |
Fe1—Fe2 | 2.5443 (14) | C36—C35 | 1.372 (5) |
Fe2—C12 | 1.769 (5) | C32—C33 | 1.380 (5) |
Fe2—C11 | 1.794 (5) | C9—O9 | 1.144 (4) |
Fe2—C13 | 1.798 (5) | C19—C24 | 1.366 (4) |
Fe2—S2 | 2.2185 (10) | C19—C20 | 1.367 (4) |
Fe2—S1 | 2.2619 (12) | C11—O11 | 1.140 (4) |
Fe3—C15 | 1.777 (5) | C7—C6 | 1.376 (4) |
Fe3—C16 | 1.783 (4) | C12—O12 | 1.147 (4) |
Fe3—C14 | 1.789 (4) | O8—C8 | 1.139 (4) |
Fe3—C1 | 2.065 (3) | C26—C27 | 1.394 (5) |
Fe3—S3 | 2.1816 (14) | C33—C34 | 1.373 (5) |
S2—C1 | 1.783 (3) | C20—C21 | 1.390 (5) |
S3—C1 | 1.788 (3) | C5—C4 | 1.363 (5) |
P—C31 | 1.810 (4) | C5—C6 | 1.387 (5) |
P—C25 | 1.829 (4) | C21—C22 | 1.365 (6) |
P—C19 | 1.835 (3) | C28—C27 | 1.343 (6) |
S1—C3 | 1.783 (4) | C34—C35 | 1.359 (5) |
C1—C2 | 1.467 (4) | C24—C23 | 1.383 (4) |
C25—C26 | 1.358 (5) | C23—C22 | 1.342 (5) |
C25—C30 | 1.383 (5) | O10—C10 | 1.140 (4) |
C16—O16 | 1.145 (4) | O13—C13 | 1.133 (4) |
C18—Fe4—C17 | 102.27 (17) | Fe1—S2—Fe4 | 142.26 (4) |
C18—Fe4—P | 89.18 (12) | C1—S3—Fe3 | 61.76 (10) |
C17—Fe4—P | 90.40 (12) | C1—S3—Fe4 | 86.33 (11) |
C18—Fe4—S3 | 157.69 (12) | Fe3—S3—Fe4 | 73.89 (3) |
C17—Fe4—S3 | 98.50 (12) | C31—P—C25 | 104.96 (18) |
P—Fe4—S3 | 98.77 (4) | C31—P—C19 | 105.73 (16) |
C18—Fe4—S2 | 94.49 (12) | C25—P—C19 | 99.78 (16) |
C17—Fe4—S2 | 94.65 (12) | C31—P—Fe4 | 114.36 (11) |
P—Fe4—S2 | 172.98 (4) | C25—P—Fe4 | 111.37 (12) |
S3—Fe4—S2 | 75.68 (4) | C19—P—Fe4 | 118.87 (14) |
C18—Fe4—Fe3 | 107.02 (12) | C3—S1—Fe1 | 112.84 (11) |
C17—Fe4—Fe3 | 149.00 (12) | C3—S1—Fe2 | 114.81 (13) |
P—Fe4—Fe3 | 99.85 (3) | Fe1—S1—Fe2 | 68.50 (4) |
S3—Fe4—Fe3 | 51.21 (3) | C2—C1—S2 | 122.0 (2) |
S2—Fe4—Fe3 | 73.36 (3) | C2—C1—S3 | 121.7 (2) |
C10—Fe1—C9 | 97.25 (19) | S2—C1—S3 | 103.89 (17) |
C10—Fe1—C8 | 89.78 (19) | C2—C1—Fe3 | 125.9 (2) |
C9—Fe1—C8 | 100.32 (19) | S2—C1—Fe3 | 101.88 (15) |
C10—Fe1—S2 | 156.24 (14) | S3—C1—Fe3 | 68.53 (11) |
C9—Fe1—S2 | 105.14 (14) | C26—C25—C30 | 118.0 (4) |
C8—Fe1—S2 | 93.88 (14) | C26—C25—P | 123.6 (4) |
C10—Fe1—S1 | 87.36 (14) | C30—C25—P | 118.5 (3) |
C9—Fe1—S1 | 99.44 (13) | O16—C16—Fe3 | 176.2 (3) |
C8—Fe1—S1 | 160.24 (14) | O15—C15—Fe3 | 176.5 (4) |
S2—Fe1—S1 | 81.30 (4) | C36—C31—C32 | 117.3 (3) |
C10—Fe1—Fe2 | 101.63 (13) | C36—C31—P | 124.1 (3) |
C9—Fe1—Fe2 | 147.54 (13) | C32—C31—P | 118.4 (3) |
C8—Fe1—Fe2 | 105.88 (14) | C4—C3—C2 | 119.4 (4) |
S2—Fe1—Fe2 | 54.82 (4) | C4—C3—S1 | 113.7 (3) |
S1—Fe1—Fe2 | 55.80 (3) | C2—C3—S1 | 126.8 (3) |
C12—Fe2—C11 | 90.34 (19) | O17—C17—Fe4 | 177.4 (4) |
C12—Fe2—C13 | 96.74 (19) | C7—C2—C3 | 117.4 (3) |
C11—Fe2—C13 | 99.5 (2) | C7—C2—C1 | 118.9 (3) |
C12—Fe2—S2 | 89.84 (12) | C3—C2—C1 | 123.7 (3) |
C11—Fe2—S2 | 158.13 (15) | O18—C18—Fe4 | 178.3 (4) |
C13—Fe2—S2 | 102.20 (14) | O14—C14—Fe3 | 175.3 (4) |
C12—Fe2—S1 | 155.48 (14) | C28—C29—C30 | 119.3 (5) |
C11—Fe2—S1 | 89.24 (13) | C35—C36—C31 | 121.5 (4) |
C13—Fe2—S1 | 107.51 (14) | C33—C32—C31 | 121.0 (4) |
S2—Fe2—S1 | 81.68 (4) | O9—C9—Fe1 | 177.3 (4) |
C12—Fe2—Fe1 | 100.67 (13) | C24—C19—C20 | 117.6 (3) |
C11—Fe2—Fe1 | 103.00 (14) | C24—C19—P | 122.4 (3) |
C13—Fe2—Fe1 | 151.31 (14) | C20—C19—P | 120.0 (3) |
S2—Fe2—Fe1 | 55.56 (3) | O11—C11—Fe2 | 177.7 (4) |
S1—Fe2—Fe1 | 55.70 (3) | C6—C7—C2 | 122.8 (4) |
C15—Fe3—C16 | 97.21 (17) | O12—C12—Fe2 | 179.6 (4) |
C15—Fe3—C14 | 91.57 (17) | C25—C26—C27 | 120.4 (4) |
C16—Fe3—C14 | 98.44 (17) | C34—C33—C32 | 119.7 (4) |
C15—Fe3—C1 | 94.39 (14) | C19—C20—C21 | 121.4 (4) |
C16—Fe3—C1 | 106.34 (14) | C4—C5—C6 | 120.1 (4) |
C14—Fe3—C1 | 153.53 (16) | C7—C6—C5 | 118.7 (4) |
C15—Fe3—S3 | 119.19 (11) | C25—C30—C29 | 121.2 (4) |
C16—Fe3—S3 | 135.10 (12) | C5—C4—C3 | 121.6 (4) |
C14—Fe3—S3 | 105.38 (13) | O8—C8—Fe1 | 176.8 (4) |
C1—Fe3—S3 | 49.71 (9) | C22—C21—C20 | 119.2 (4) |
C15—Fe3—Fe4 | 164.89 (11) | C27—C28—C29 | 119.8 (5) |
C16—Fe3—Fe4 | 83.02 (12) | C35—C34—C33 | 120.5 (5) |
C14—Fe3—Fe4 | 103.36 (12) | C28—C27—C26 | 121.2 (5) |
C1—Fe3—Fe4 | 71.20 (9) | C19—C24—C23 | 121.4 (4) |
S3—Fe3—Fe4 | 54.90 (3) | C22—C23—C24 | 120.2 (5) |
C1—S2—Fe2 | 119.57 (10) | C34—C35—C36 | 120.1 (4) |
C1—S2—Fe1 | 113.55 (11) | C23—C22—C21 | 120.1 (4) |
Fe2—S2—Fe1 | 69.62 (4) | O10—C10—Fe1 | 178.0 (4) |
C1—S2—Fe4 | 86.30 (11) | O13—C13—Fe2 | 176.1 (4) |
Fe2—S2—Fe4 | 129.55 (5) | ||
P—Fe4—Fe3—C15 | −165.0 (5) | P—Fe4—Fe3—C1 | −146.83 (10) |
P—Fe4—Fe3—C16 | 103.23 (11) | P—Fe4—Fe3—S3 | −93.39 (5) |
P—Fe4—Fe3—C14 | 6.18 (14) |
Experimental details
Crystal data | |
Chemical formula | [Fe4C7H4S3)(C18H15P)(CO)11] |
Mr | 978.09 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 293 |
a, b, c (Å) | 9.725 (5), 17.954 (5), 22.885 (5) |
β (°) | 98.488 (5) |
V (Å3) | 3952 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.70 |
Crystal size (mm) | 0.3 × 0.2 × 0.1 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Part of the refinement model (ΔF) (Walker et al., 1983) |
Tmin, Tmax | 0.618, 0.887 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 28122, 6888, 3440 |
Rint | 0.090 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.055, 0.80 |
No. of reflections | 6888 |
No. of parameters | 496 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.27, −0.34 |
Computer programs: KappaCCD Reference Manual (Nonius, 1998), DENZO and SCALEPACK (Otwinowski & Minor, 1997), DENZO and SCALEPACK, SIR97 (Altomare et al., 1998), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), WinGX (Farrugia, 1999).
Fe4—P | 2.2645 (11) | Fe2—S2 | 2.2185 (10) |
Fe4—S3 | 2.2901 (11) | Fe2—S1 | 2.2619 (12) |
Fe4—S2 | 2.2946 (11) | Fe3—C1 | 2.065 (3) |
Fe4—Fe3 | 2.6890 (10) | Fe3—S3 | 2.1816 (14) |
Fe1—S2 | 2.2385 (13) | S1—C3 | 1.783 (4) |
Fe1—S1 | 2.2592 (11) | C1—C2 | 1.467 (4) |
Fe1—Fe2 | 2.5443 (14) | ||
P—Fe4—S3 | 98.77 (4) | P—Fe4—Fe3 | 99.85 (3) |
P—Fe4—S2 | 172.98 (4) | S3—Fe4—Fe3 | 51.21 (3) |
S3—Fe4—S2 | 75.68 (4) | S2—Fe4—Fe3 | 73.36 (3) |
P—Fe4—Fe3—C15 | −165.0 (5) | P—Fe4—Fe3—C1 | −146.83 (10) |
P—Fe4—Fe3—C16 | 103.23 (11) | P—Fe4—Fe3—S3 | −93.39 (5) |
P—Fe4—Fe3—C14 | 6.18 (14) |
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L'intérêt des complexes organométalliques se situe surtout dans la synthèse organique (Alper et al., 1978), de la synthèse bioinorganique (Jaouen et al., 1993), et dans des processus catalytiques (Tolman et al., 1972). Le remplacement du carbonyle par d'autres ligands isoélectroniques L [L = P(OMe)3, PPh3, t-BuNC, etc.] dans les complexes des métaux de transition constitue l'une des réactions fondamentales de la chimie organométallique. Les réactions de remplacement du monoxyde de carbone catalysés par transfert d'électrons dans des complexes polynucléaires du fer à ligands soufrés ont déjà été étudiées (Darchen et al., 1982). Dans la plupart des cas, la substitution induite à l'électrode conduit aux mêmes résultats que ceux obtenus par voie thermique (Darchen et al., 1983), toutefois pour certains substrats on observe une activation différente des carbonyles suivant la voie de synthèse utilisée. Ainsi dans le complexe non symétrique (µ-ROCS) (µ-MeS)(Fe2(CO)6 (Patin et al., 1980, 1981) le ligand P(OMe)3 occupe la position située dans le prolongement de la liaison Fe—Fe lorsqu'il est introduit par voie thermique (Patin et al., 1989). Afin d'étudier la stéréospécificité et la régioselectivité du remplacement des carbonyles par d'autres ligands plus donneurs L [L = P(Ph)3 ou P(OMe)3], une étude par diffraction des rayons X sur le complexe monosubstitué (Fe4S3C36O11PH19) est réalisée.
Le complexe TN (Bird et al., 1981) contient deux motifs binucléaires A et B différents et trois sites métalliques non équivalents qui font de ce complexe un substrat de choix pour l'étude de la régiosélectivité et la stéréosélectivité du remplacement de carbonyles. Les deux motifs binucléaires sont analogues à ceux observés dans les complexes (µ-ROCS)(µ-MeS)(Fe2(CO)6) où la régiosélectivité de la substitution de carbonyles semble être dépendante du mode d'activation (Jahrani, 1994). Le complexe (Fe4S3C36O11PH19) contient deux motifs binucléaires A et B différents, liés entre eux par le ligand C6SCS2. le motif A est pseudosymétrique et le squelette Fe2(CO)6 est doublement ponté par les deux atomes de soufre S1 et S2 du ligand. Le motif B est asymétrique, seul l'atome S3 du ligand ponte les deux atomes de fer alors que S2 qui ponte le motif A est uniquement lié à l'atome Fe4 du motif B. Cette structure montre que la substitution du carbonyle par la triphenylphosphine a lieu spécifiquement sur le motif B asymétyrique, le moins encombré, ponté par CS2 en position équatoriale par rapport à la liaison Fe3—Fe4 [Fe3—Fe4—P = 99.86 (3)°]. L'allongement de la liaison métallique Fe3—Fe4 de 0.057 Å par rapport au complexe non substitué TN est certainement lié á l'effet σ donneur du ligand PPh3.