Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803008638/dn6067sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803008638/dn6067Isup2.hkl |
CCDC reference: 214577
Le complexe tétranucléaire disubstitué (Fe4S3C23O16P2H22) est préparé sous activation thermique du TN, où un carbonyle du motif A symétrique et un carbonyle du motif B asymétrique sont substitués par le ligand trimethyl phosphite, 5,9x10−4 moles de TN et 1,2 × 10−3 moles de P(OMe)3 sont dissouts dans l'acétone et chauffés à reflux pendant 10 heures sous azote et à l'abri de la lumière. La réaction conduit en premier temps au monosubstitué qui réagit à son tour avec l'éxcès du P(OMe)3 pour conduire au complexe disubstitué. Le solvant est distillé et le résidu est séparé par chromatographie préparative sur plaque (éluant: éther de pétrole/éther éthylique 8:1). Le complexe disubstitué (Fe4S3C23O16PH18) est récupéré aprés lavage du gel de silice à l'acétone puis recristallisé dans l'éther/hexane 1:1), on obtient des cristaux rouges prismatiques.
Data collection: CAD-4 EXPRESS (Enraf-Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SIR2002 (Burla et al., 2003); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Fig. 1. Dessin ORTEP-3 (Farrugia, 1997) de la molécule. Les ellipsoides de vibration des atomes ont une probabilité de 50%. |
[Fe4(C3H9O3P)2(C7H4S3)(CO)10] | F(000) = 1880 |
Mr = 935.96 | Dx = 1.764 Mg m−3 |
Monoclinic, P21/c | Melting point: 172 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 16.4390 (2) Å | Cell parameters from 25 reflections |
b = 8.9990 (3) Å | θ = 10–15° |
c = 23.9750 (2) Å | µ = 1.95 mm−1 |
β = 96.529 (3)° | T = 293 K |
V = 3523.73 (13) Å3 | Prism, red |
Z = 4 | 0.1 × 0.1 × 0.05 mm |
Enraf-Nonius CAD-4 diffractometer | 5439 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.006 |
Graphite monochromator | θmax = 26.0°, θmin = 2.4° |
non–profiled ω scans | h = 0→20 |
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983) | k = −11→0 |
Tmin = 0.818, Tmax = 0.907 | l = −29→29 |
7804 measured reflections | 3 standard reflections every 120 min |
6840 independent reflections | intensity decay: 3% |
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)] = 0.029 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0302P)2 + 2.4041P] where P = (Fo2 + 2Fc2)/3 |
6840 reflections | (Δ/σ)max = 0.001 |
439 parameters | Δρmax = 0.88 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
[Fe4(C3H9O3P)2(C7H4S3)(CO)10] | V = 3523.73 (13) Å3 |
Mr = 935.96 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 16.4390 (2) Å | µ = 1.95 mm−1 |
b = 8.9990 (3) Å | T = 293 K |
c = 23.9750 (2) Å | 0.1 × 0.1 × 0.05 mm |
β = 96.529 (3)° |
Enraf-Nonius CAD-4 diffractometer | 5439 reflections with I > 2σ(I) |
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983) | Rint = 0.006 |
Tmin = 0.818, Tmax = 0.907 | 3 standard reflections every 120 min |
7804 measured reflections | intensity decay: 3% |
6840 independent reflections |
R[F2 > 2σ(F2)] = 0.029 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.88 e Å−3 |
6840 reflections | Δρmin = −0.27 e Å−3 |
439 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 | 0.76290 (2) | −0.00444 (5) | 0.444371 (15) | 0.03405 (10) | |
Fe2 | 0.80230 (2) | 0.07918 (4) | 0.283024 (15) | 0.03270 (10) | |
Fe1 | 0.79409 (2) | 0.33984 (4) | 0.325608 (16) | 0.03439 (10) | |
Fe3 | 0.63667 (3) | 0.18250 (5) | 0.447769 (17) | 0.04380 (12) | |
S2 | 0.75392 (4) | 0.12990 (7) | 0.36268 (3) | 0.03065 (14) | |
S1 | 0.71198 (4) | 0.25515 (8) | 0.25075 (3) | 0.03809 (16) | |
P2 | 0.74270 (5) | −0.11885 (10) | 0.52125 (3) | 0.04369 (19) | |
P1 | 0.85180 (5) | 0.07617 (9) | 0.20256 (3) | 0.04316 (19) | |
O21 | 0.79639 (15) | −0.2602 (3) | 0.53904 (10) | 0.0645 (7) | |
O22 | 0.65508 (14) | −0.1905 (3) | 0.52530 (9) | 0.0529 (6) | |
O19 | 0.80124 (17) | −0.0090 (3) | 0.15257 (10) | 0.0695 (7) | |
O23 | 0.75084 (16) | −0.0126 (3) | 0.57373 (9) | 0.0630 (7) | |
O18 | 0.87479 (16) | 0.2303 (3) | 0.17949 (9) | 0.0619 (7) | |
O17 | 0.91101 (16) | 0.1346 (3) | 0.49995 (11) | 0.0725 (8) | |
O14 | 0.76774 (17) | 0.3887 (3) | 0.48772 (12) | 0.0757 (8) | |
O10 | 0.68105 (16) | 0.5599 (3) | 0.36427 (11) | 0.0652 (7) | |
C3 | 0.61045 (17) | 0.2184 (3) | 0.26613 (12) | 0.0404 (7) | |
O20 | 0.93739 (15) | −0.0088 (3) | 0.20017 (11) | 0.0637 (7) | |
O11 | 0.73815 (16) | −0.2213 (3) | 0.26874 (11) | 0.0686 (7) | |
O8 | 0.87576 (16) | 0.5267 (3) | 0.24892 (11) | 0.0691 (7) | |
O16 | 0.84553 (16) | −0.2562 (3) | 0.39805 (11) | 0.0678 (7) | |
C17 | 0.8521 (2) | 0.0827 (4) | 0.47903 (12) | 0.0457 (7) | |
O9 | 0.93293 (16) | 0.3850 (3) | 0.41159 (11) | 0.0783 (8) | |
C13 | 0.6018 (2) | 0.1498 (5) | 0.51519 (15) | 0.0632 (10) | |
O12 | 0.96298 (15) | 0.0281 (3) | 0.34428 (11) | 0.0687 (7) | |
O15 | 0.51202 (19) | 0.4075 (4) | 0.41617 (13) | 0.0924 (10) | |
C2 | 0.58772 (17) | 0.1604 (3) | 0.31622 (12) | 0.0397 (6) | |
C22 | 0.6274 (2) | −0.3194 (4) | 0.49328 (15) | 0.0605 (9) | |
H22A | 0.6616 | −0.3349 | 0.4639 | 0.091* | |
H22B | 0.5718 | −0.3048 | 0.4771 | 0.091* | |
H22C | 0.6303 | −0.4048 | 0.5174 | 0.091* | |
C4 | 0.5510 (2) | 0.2482 (4) | 0.22167 (14) | 0.0562 (9) | |
H4 | 0.5664 | 0.2880 | 0.1886 | 0.067* | |
O13 | 0.5763 (2) | 0.1359 (4) | 0.55720 (11) | 0.0968 (11) | |
C19 | 0.7157 (3) | 0.0236 (6) | 0.13496 (17) | 0.0932 (16) | |
H19A | 0.6838 | 0.0016 | 0.1651 | 0.140* | |
H19B | 0.6969 | −0.0360 | 0.1029 | 0.140* | |
H19C | 0.7099 | 0.1269 | 0.1253 | 0.140* | |
C5 | 0.4698 (2) | 0.2197 (5) | 0.22574 (16) | 0.0707 (11) | |
H5 | 0.4305 | 0.2408 | 0.1957 | 0.085* | |
C14 | 0.7192 (2) | 0.3053 (4) | 0.47116 (14) | 0.0550 (8) | |
C15 | 0.5590 (2) | 0.3164 (4) | 0.42831 (15) | 0.0610 (9) | |
C16 | 0.81208 (19) | −0.1596 (4) | 0.41623 (12) | 0.0430 (7) | |
C6 | 0.4468 (2) | 0.1601 (5) | 0.27430 (17) | 0.0713 (11) | |
H6 | 0.3920 | 0.1391 | 0.2770 | 0.086* | |
C7 | 0.50442 (19) | 0.1314 (4) | 0.31873 (15) | 0.0564 (9) | |
H7 | 0.4879 | 0.0917 | 0.3515 | 0.068* | |
C11 | 0.76216 (18) | −0.1024 (4) | 0.27324 (12) | 0.0410 (7) | |
C9 | 0.8786 (2) | 0.3647 (4) | 0.37881 (13) | 0.0470 (7) | |
C1 | 0.64672 (16) | 0.1255 (3) | 0.36597 (11) | 0.0348 (6) | |
C8 | 0.8441 (2) | 0.4542 (3) | 0.27815 (13) | 0.0460 (7) | |
C23 | 0.7347 (3) | −0.0624 (6) | 0.62907 (14) | 0.0963 (16) | |
H23A | 0.6780 | −0.0889 | 0.6282 | 0.144* | |
H23B | 0.7473 | 0.0162 | 0.6557 | 0.144* | |
H23C | 0.7682 | −0.1473 | 0.6399 | 0.144* | |
C12 | 0.9002 (2) | 0.0462 (3) | 0.31970 (12) | 0.0440 (7) | |
C10 | 0.72527 (19) | 0.4757 (3) | 0.34981 (13) | 0.0439 (7) | |
C18 | 0.9063 (3) | 0.2465 (5) | 0.12553 (15) | 0.0925 (15) | |
H18A | 0.9614 | 0.2100 | 0.1283 | 0.139* | |
H18B | 0.9055 | 0.3496 | 0.1151 | 0.139* | |
H18C | 0.8727 | 0.1908 | 0.0976 | 0.139* | |
C20 | 0.9440 (3) | −0.1629 (4) | 0.21242 (17) | 0.0690 (11) | |
H20A | 0.9350 | −0.1795 | 0.2508 | 0.103* | |
H20B | 0.9978 | −0.1971 | 0.2067 | 0.103* | |
H20C | 0.9039 | −0.2165 | 0.1881 | 0.103* | |
C21 | 0.8839 (2) | −0.2621 (6) | 0.54557 (19) | 0.0947 (16) | |
H21A | 0.9034 | −0.2418 | 0.5101 | 0.142* | |
H21B | 0.9030 | −0.3581 | 0.5587 | 0.142* | |
H21C | 0.9042 | −0.1877 | 0.5723 | 0.142* | |
S3 | 0.63088 (4) | −0.03414 (9) | 0.40670 (3) | 0.04137 (17) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe4 | 0.0334 (2) | 0.0367 (2) | 0.03162 (19) | 0.00256 (18) | 0.00186 (15) | 0.00352 (16) |
Fe2 | 0.0350 (2) | 0.0303 (2) | 0.03301 (19) | −0.00111 (17) | 0.00448 (15) | 0.00064 (16) |
Fe1 | 0.0343 (2) | 0.0295 (2) | 0.0388 (2) | −0.00182 (17) | 0.00194 (16) | 0.00149 (16) |
Fe3 | 0.0405 (2) | 0.0494 (3) | 0.0430 (2) | 0.0093 (2) | 0.01113 (18) | 0.0037 (2) |
S2 | 0.0296 (3) | 0.0313 (3) | 0.0305 (3) | 0.0008 (3) | 0.0015 (2) | 0.0019 (3) |
S1 | 0.0411 (4) | 0.0371 (4) | 0.0348 (3) | −0.0008 (3) | −0.0011 (3) | 0.0056 (3) |
P2 | 0.0479 (5) | 0.0480 (5) | 0.0352 (4) | 0.0051 (4) | 0.0048 (3) | 0.0074 (3) |
P1 | 0.0558 (5) | 0.0366 (4) | 0.0390 (4) | −0.0051 (4) | 0.0136 (3) | −0.0020 (3) |
O21 | 0.0599 (15) | 0.0706 (17) | 0.0634 (14) | 0.0205 (13) | 0.0094 (12) | 0.0271 (13) |
O22 | 0.0557 (14) | 0.0544 (14) | 0.0515 (12) | −0.0019 (11) | 0.0184 (10) | 0.0052 (11) |
O19 | 0.0834 (19) | 0.0752 (18) | 0.0507 (13) | −0.0152 (15) | 0.0108 (13) | −0.0183 (12) |
O23 | 0.0864 (18) | 0.0669 (16) | 0.0352 (11) | −0.0054 (14) | 0.0043 (11) | −0.0010 (11) |
O18 | 0.0953 (19) | 0.0472 (14) | 0.0467 (12) | −0.0135 (13) | 0.0237 (12) | 0.0034 (10) |
O17 | 0.0582 (16) | 0.090 (2) | 0.0650 (15) | −0.0183 (15) | −0.0130 (13) | −0.0078 (14) |
O14 | 0.0707 (18) | 0.0669 (18) | 0.0872 (19) | −0.0001 (15) | −0.0009 (15) | −0.0274 (15) |
O10 | 0.0655 (16) | 0.0542 (15) | 0.0772 (17) | 0.0216 (13) | 0.0141 (13) | −0.0025 (13) |
C3 | 0.0359 (15) | 0.0372 (16) | 0.0455 (15) | −0.0009 (13) | −0.0062 (12) | 0.0067 (13) |
O20 | 0.0665 (16) | 0.0559 (15) | 0.0741 (16) | 0.0022 (13) | 0.0316 (13) | 0.0045 (12) |
O11 | 0.0654 (16) | 0.0463 (15) | 0.0929 (19) | −0.0197 (13) | 0.0035 (14) | −0.0022 (13) |
O8 | 0.0765 (18) | 0.0563 (15) | 0.0764 (17) | −0.0147 (14) | 0.0165 (14) | 0.0217 (13) |
O16 | 0.0768 (18) | 0.0514 (15) | 0.0761 (16) | 0.0156 (14) | 0.0131 (14) | −0.0114 (13) |
C17 | 0.0482 (18) | 0.0517 (19) | 0.0364 (15) | 0.0042 (16) | 0.0018 (13) | 0.0030 (14) |
O9 | 0.0564 (16) | 0.094 (2) | 0.0778 (17) | −0.0130 (15) | −0.0233 (14) | 0.0029 (16) |
C13 | 0.060 (2) | 0.075 (3) | 0.058 (2) | 0.021 (2) | 0.0188 (18) | 0.0061 (18) |
O12 | 0.0436 (14) | 0.0779 (18) | 0.0806 (17) | 0.0088 (13) | −0.0096 (13) | 0.0040 (14) |
O15 | 0.080 (2) | 0.094 (2) | 0.105 (2) | 0.0491 (19) | 0.0188 (17) | 0.0151 (18) |
C2 | 0.0350 (15) | 0.0365 (16) | 0.0462 (15) | 0.0002 (13) | −0.0017 (12) | 0.0043 (13) |
C22 | 0.061 (2) | 0.055 (2) | 0.066 (2) | −0.0053 (18) | 0.0110 (18) | 0.0078 (18) |
C4 | 0.052 (2) | 0.060 (2) | 0.0523 (18) | −0.0045 (17) | −0.0133 (15) | 0.0160 (16) |
O13 | 0.106 (2) | 0.130 (3) | 0.0628 (17) | 0.032 (2) | 0.0443 (17) | 0.0189 (18) |
C19 | 0.087 (3) | 0.122 (4) | 0.064 (2) | 0.013 (3) | −0.022 (2) | −0.030 (3) |
C5 | 0.046 (2) | 0.083 (3) | 0.076 (2) | −0.005 (2) | −0.0250 (18) | 0.023 (2) |
C14 | 0.057 (2) | 0.059 (2) | 0.0498 (18) | 0.0125 (18) | 0.0071 (16) | −0.0094 (16) |
C15 | 0.057 (2) | 0.067 (2) | 0.062 (2) | 0.014 (2) | 0.0185 (17) | 0.0037 (18) |
C16 | 0.0435 (17) | 0.0439 (18) | 0.0408 (15) | −0.0002 (15) | 0.0011 (13) | 0.0065 (13) |
C6 | 0.0360 (19) | 0.087 (3) | 0.086 (3) | −0.0062 (19) | −0.0136 (18) | 0.027 (2) |
C7 | 0.0349 (17) | 0.066 (2) | 0.067 (2) | −0.0038 (16) | −0.0027 (15) | 0.0173 (18) |
C11 | 0.0368 (16) | 0.0428 (18) | 0.0437 (15) | −0.0013 (14) | 0.0059 (12) | 0.0012 (13) |
C9 | 0.0461 (18) | 0.0425 (18) | 0.0516 (18) | −0.0035 (15) | 0.0027 (15) | 0.0030 (14) |
C1 | 0.0279 (14) | 0.0387 (15) | 0.0378 (14) | −0.0001 (12) | 0.0032 (11) | 0.0047 (12) |
C8 | 0.0481 (18) | 0.0353 (17) | 0.0539 (18) | −0.0018 (14) | 0.0030 (15) | 0.0028 (14) |
C23 | 0.145 (5) | 0.110 (4) | 0.0361 (18) | −0.001 (3) | 0.021 (2) | 0.002 (2) |
C12 | 0.0449 (18) | 0.0411 (17) | 0.0470 (16) | 0.0017 (14) | 0.0097 (14) | 0.0019 (13) |
C10 | 0.0453 (18) | 0.0379 (16) | 0.0473 (17) | −0.0012 (15) | 0.0004 (14) | 0.0018 (13) |
C18 | 0.148 (4) | 0.082 (3) | 0.055 (2) | −0.029 (3) | 0.043 (3) | 0.010 (2) |
C20 | 0.074 (3) | 0.046 (2) | 0.092 (3) | 0.0116 (19) | 0.029 (2) | −0.0016 (19) |
C21 | 0.058 (3) | 0.133 (4) | 0.090 (3) | 0.028 (3) | −0.006 (2) | 0.045 (3) |
S3 | 0.0354 (4) | 0.0441 (4) | 0.0440 (4) | −0.0042 (3) | 0.0021 (3) | 0.0108 (3) |
Fe4—C17 | 1.782 (3) | C3—C4 | 1.388 (4) |
Fe4—C16 | 1.784 (3) | C3—C2 | 1.399 (4) |
Fe4—P2 | 2.1695 (8) | O20—C20 | 1.420 (4) |
Fe4—S3 | 2.2697 (8) | O11—C11 | 1.141 (4) |
Fe4—S2 | 2.2920 (7) | O8—C8 | 1.128 (4) |
Fe4—Fe3 | 2.6798 (6) | O16—C16 | 1.141 (4) |
Fe2—C11 | 1.768 (3) | O9—C9 | 1.135 (4) |
Fe2—C12 | 1.770 (3) | C13—O13 | 1.141 (4) |
Fe2—P1 | 2.1776 (8) | O12—C12 | 1.140 (4) |
Fe2—S2 | 2.1986 (7) | O15—C15 | 1.141 (4) |
Fe2—S1 | 2.2472 (8) | C2—C7 | 1.402 (4) |
Fe2—Fe1 | 2.5679 (5) | C2—C1 | 1.483 (4) |
Fe1—C9 | 1.790 (3) | C22—H22A | 0.9600 |
Fe1—C8 | 1.800 (3) | C22—H22B | 0.9600 |
Fe1—C10 | 1.806 (3) | C22—H22C | 0.9600 |
Fe1—S2 | 2.2201 (8) | C4—C5 | 1.374 (5) |
Fe1—S1 | 2.2522 (8) | C4—H4 | 0.9300 |
Fe3—C15 | 1.779 (4) | C19—H19A | 0.9600 |
Fe3—C14 | 1.790 (4) | C19—H19B | 0.9600 |
Fe3—C13 | 1.800 (4) | C19—H19C | 0.9600 |
Fe3—C1 | 2.052 (3) | C5—C6 | 1.373 (5) |
Fe3—S3 | 2.1813 (9) | C5—H5 | 0.9300 |
S2—C1 | 1.773 (3) | C6—C7 | 1.367 (5) |
S1—C3 | 1.781 (3) | C6—H6 | 0.9300 |
P2—O23 | 1.574 (2) | C7—H7 | 0.9300 |
P2—O21 | 1.579 (2) | C1—S3 | 1.773 (3) |
P2—O22 | 1.591 (2) | C23—H23A | 0.9600 |
P1—O18 | 1.556 (2) | C23—H23B | 0.9600 |
P1—O19 | 1.577 (2) | C23—H23C | 0.9600 |
P1—O20 | 1.608 (3) | C18—H18A | 0.9600 |
O21—C21 | 1.430 (4) | C18—H18B | 0.9600 |
O22—C22 | 1.437 (4) | C18—H18C | 0.9600 |
O19—C19 | 1.451 (5) | C20—H20A | 0.9600 |
O23—C23 | 1.453 (4) | C20—H20B | 0.9600 |
O18—C18 | 1.454 (4) | C20—H20C | 0.9600 |
O17—C17 | 1.140 (4) | C21—H21A | 0.9600 |
O14—C14 | 1.134 (4) | C21—H21B | 0.9600 |
O10—C10 | 1.131 (4) | C21—H21C | 0.9600 |
C17—Fe4—C16 | 97.86 (14) | O20—P1—Fe2 | 117.01 (10) |
C17—Fe4—P2 | 90.57 (10) | C21—O21—P2 | 124.3 (3) |
C16—Fe4—P2 | 93.99 (10) | C22—O22—P2 | 121.9 (2) |
C17—Fe4—S3 | 159.35 (11) | C19—O19—P1 | 122.1 (3) |
C16—Fe4—S3 | 102.19 (10) | C23—O23—P2 | 122.3 (3) |
P2—Fe4—S3 | 92.89 (3) | C18—O18—P1 | 122.1 (2) |
C17—Fe4—S2 | 97.81 (10) | C4—C3—C2 | 119.9 (3) |
C16—Fe4—S2 | 94.45 (9) | C4—C3—S1 | 113.6 (2) |
P2—Fe4—S2 | 167.17 (3) | C2—C3—S1 | 126.5 (2) |
S3—Fe4—S2 | 75.89 (3) | C20—O20—P1 | 120.3 (2) |
C17—Fe4—Fe3 | 107.95 (11) | O17—C17—Fe4 | 177.1 (3) |
C16—Fe4—Fe3 | 152.70 (10) | O13—C13—Fe3 | 175.8 (3) |
P2—Fe4—Fe3 | 94.49 (3) | C3—C2—C7 | 117.6 (3) |
S3—Fe4—Fe3 | 51.49 (2) | C3—C2—C1 | 123.7 (3) |
S2—Fe4—Fe3 | 73.74 (2) | C7—C2—C1 | 118.6 (3) |
C11—Fe2—C12 | 102.46 (14) | O22—C22—H22A | 109.5 |
C11—Fe2—P1 | 92.43 (10) | O22—C22—H22B | 109.5 |
C12—Fe2—P1 | 91.58 (10) | H22A—C22—H22B | 109.5 |
C11—Fe2—S2 | 98.09 (10) | O22—C22—H22C | 109.5 |
C12—Fe2—S2 | 90.10 (10) | H22A—C22—H22C | 109.5 |
P1—Fe2—S2 | 168.73 (3) | H22B—C22—H22C | 109.5 |
C11—Fe2—S1 | 112.56 (10) | C5—C4—C3 | 121.0 (3) |
C12—Fe2—S1 | 144.83 (11) | C5—C4—H4 | 119.5 |
P1—Fe2—S1 | 90.15 (3) | C3—C4—H4 | 119.5 |
S2—Fe2—S1 | 82.10 (3) | O19—C19—H19A | 109.5 |
C11—Fe2—Fe1 | 149.47 (10) | O19—C19—H19B | 109.5 |
C12—Fe2—Fe1 | 92.38 (10) | H19A—C19—H19B | 109.5 |
P1—Fe2—Fe1 | 113.92 (3) | O19—C19—H19C | 109.5 |
S2—Fe2—Fe1 | 54.86 (2) | H19A—C19—H19C | 109.5 |
S1—Fe2—Fe1 | 55.29 (2) | H19B—C19—H19C | 109.5 |
C9—Fe1—C8 | 90.32 (14) | C6—C5—C4 | 119.8 (3) |
C9—Fe1—C10 | 98.63 (14) | C6—C5—H5 | 120.1 |
C8—Fe1—C10 | 99.41 (14) | C4—C5—H5 | 120.1 |
C9—Fe1—S2 | 93.64 (10) | O14—C14—Fe3 | 175.3 (3) |
C8—Fe1—S2 | 156.54 (10) | O15—C15—Fe3 | 176.7 (4) |
C10—Fe1—S2 | 102.82 (10) | O16—C16—Fe4 | 177.9 (3) |
C9—Fe1—S1 | 163.02 (11) | C7—C6—C5 | 120.1 (3) |
C8—Fe1—S1 | 88.00 (10) | C7—C6—H6 | 120.0 |
C10—Fe1—S1 | 98.31 (10) | C5—C6—H6 | 120.0 |
S2—Fe1—S1 | 81.52 (3) | C6—C7—C2 | 121.7 (3) |
C9—Fe1—Fe2 | 109.03 (11) | C6—C7—H7 | 119.2 |
C8—Fe1—Fe2 | 102.86 (10) | C2—C7—H7 | 119.2 |
C10—Fe1—Fe2 | 144.05 (10) | O11—C11—Fe2 | 177.4 (3) |
S2—Fe1—Fe2 | 54.08 (2) | O9—C9—Fe1 | 177.6 (3) |
S1—Fe1—Fe2 | 55.11 (2) | C2—C1—S3 | 119.4 (2) |
C15—Fe3—C14 | 99.20 (17) | C2—C1—S2 | 121.5 (2) |
C15—Fe3—C13 | 93.09 (16) | S3—C1—S2 | 104.57 (14) |
C14—Fe3—C13 | 97.29 (17) | C2—C1—Fe3 | 126.8 (2) |
C15—Fe3—C1 | 92.99 (14) | S3—C1—Fe3 | 69.10 (9) |
C14—Fe3—C1 | 108.25 (13) | S2—C1—Fe3 | 103.02 (13) |
C13—Fe3—C1 | 152.39 (16) | O8—C8—Fe1 | 179.2 (3) |
C15—Fe3—S3 | 119.60 (13) | O23—C23—H23A | 109.5 |
C14—Fe3—S3 | 133.30 (11) | O23—C23—H23B | 109.5 |
C13—Fe3—S3 | 104.92 (14) | H23A—C23—H23B | 109.5 |
C1—Fe3—S3 | 49.40 (8) | O23—C23—H23C | 109.5 |
C15—Fe3—Fe4 | 162.26 (11) | H23A—C23—H23C | 109.5 |
C14—Fe3—Fe4 | 80.50 (11) | H23B—C23—H23C | 109.5 |
C13—Fe3—Fe4 | 104.56 (12) | O12—C12—Fe2 | 178.1 (3) |
C1—Fe3—Fe4 | 70.56 (8) | O10—C10—Fe1 | 178.7 (3) |
S3—Fe3—Fe4 | 54.51 (2) | O18—C18—H18A | 109.5 |
C1—S2—Fe2 | 119.56 (9) | O18—C18—H18B | 109.5 |
C1—S2—Fe1 | 112.28 (10) | H18A—C18—H18B | 109.5 |
Fe2—S2—Fe1 | 71.06 (2) | O18—C18—H18C | 109.5 |
C1—S2—Fe4 | 85.30 (9) | H18A—C18—H18C | 109.5 |
Fe2—S2—Fe4 | 129.66 (3) | H18B—C18—H18C | 109.5 |
Fe1—S2—Fe4 | 142.92 (3) | O20—C20—H20A | 109.5 |
C3—S1—Fe2 | 113.33 (10) | O20—C20—H20B | 109.5 |
C3—S1—Fe1 | 112.88 (10) | H20A—C20—H20B | 109.5 |
Fe2—S1—Fe1 | 69.60 (2) | O20—C20—H20C | 109.5 |
O23—P2—O21 | 106.22 (14) | H20A—C20—H20C | 109.5 |
O23—P2—O22 | 101.11 (13) | H20B—C20—H20C | 109.5 |
O21—P2—O22 | 98.00 (13) | O21—C21—H21A | 109.5 |
O23—P2—Fe4 | 112.55 (10) | O21—C21—H21B | 109.5 |
O21—P2—Fe4 | 118.48 (9) | H21A—C21—H21B | 109.5 |
O22—P2—Fe4 | 118.12 (9) | O21—C21—H21C | 109.5 |
O18—P1—O19 | 106.94 (14) | H21A—C21—H21C | 109.5 |
O18—P1—O20 | 99.33 (14) | H21B—C21—H21C | 109.5 |
O19—P1—O20 | 97.45 (15) | C1—S3—Fe3 | 61.50 (9) |
O18—P1—Fe2 | 115.74 (9) | C1—S3—Fe4 | 85.99 (9) |
O19—P1—Fe2 | 117.48 (10) | Fe3—S3—Fe4 | 74.01 (3) |
Experimental details
Crystal data | |
Chemical formula | [Fe4(C3H9O3P)2(C7H4S3)(CO)10] |
Mr | 935.96 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 16.4390 (2), 8.9990 (3), 23.9750 (2) |
β (°) | 96.529 (3) |
V (Å3) | 3523.73 (13) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.95 |
Crystal size (mm) | 0.1 × 0.1 × 0.05 |
Data collection | |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Part of the refinement model (ΔF) (Walker & Stuart, 1983) |
Tmin, Tmax | 0.818, 0.907 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7804, 6840, 5439 |
Rint | 0.006 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.076, 1.05 |
No. of reflections | 6840 |
No. of parameters | 439 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.88, −0.27 |
Computer programs: CAD-4 EXPRESS (Enraf-Nonius, 1994), CAD-4 EXPRESS, XCAD4 (Harms & Wocadlo, 1995), SIR2002 (Burla et al., 2003), SHELXL97 (Sheldrick, 1997), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Fe4—P2 | 2.1695 (8) | Fe3—C1 | 2.052 (3) |
Fe4—S3 | 2.2697 (8) | Fe3—S3 | 2.1813 (9) |
Fe4—S2 | 2.2920 (7) | S2—C1 | 1.773 (3) |
Fe4—Fe3 | 2.6798 (6) | S1—C3 | 1.781 (3) |
Fe2—P1 | 2.1776 (8) | C3—C4 | 1.388 (4) |
Fe2—S2 | 2.1986 (7) | C3—C2 | 1.399 (4) |
Fe2—Fe1 | 2.5679 (5) | C2—C7 | 1.402 (4) |
Fe1—S2 | 2.2201 (8) | C2—C1 | 1.483 (4) |
Fe1—S1 | 2.2522 (8) | C1—S3 | 1.773 (3) |
P2—Fe4—S3 | 92.89 (3) | Fe1—S2—Fe4 | 142.92 (3) |
P2—Fe4—S2 | 167.17 (3) | C3—S1—Fe2 | 113.33 (10) |
S3—Fe4—S2 | 75.89 (3) | C3—S1—Fe1 | 112.88 (10) |
P2—Fe4—Fe3 | 94.49 (3) | Fe2—S1—Fe1 | 69.60 (2) |
S3—Fe4—Fe3 | 51.49 (2) | C4—C3—C2 | 119.9 (3) |
S2—Fe4—Fe3 | 73.74 (2) | C4—C3—S1 | 113.6 (2) |
P1—Fe2—S2 | 168.73 (3) | C2—C3—S1 | 126.5 (2) |
P1—Fe2—S1 | 90.15 (3) | C3—C2—C7 | 117.6 (3) |
S2—Fe2—S1 | 82.10 (3) | C3—C2—C1 | 123.7 (3) |
P1—Fe2—Fe1 | 113.92 (3) | C7—C2—C1 | 118.6 (3) |
S2—Fe2—Fe1 | 54.86 (2) | C5—C4—C3 | 121.0 (3) |
S1—Fe2—Fe1 | 55.29 (2) | C6—C5—C4 | 119.8 (3) |
S2—Fe1—S1 | 81.52 (3) | C7—C6—C5 | 120.1 (3) |
S2—Fe1—Fe2 | 54.08 (2) | C2—C1—S3 | 119.4 (2) |
S1—Fe1—Fe2 | 55.11 (2) | C2—C1—S2 | 121.5 (2) |
C1—Fe3—Fe4 | 70.56 (8) | S3—C1—S2 | 104.57 (14) |
S3—Fe3—Fe4 | 54.51 (2) | C2—C1—Fe3 | 126.8 (2) |
C1—S2—Fe2 | 119.56 (9) | S3—C1—Fe3 | 69.10 (9) |
C1—S2—Fe1 | 112.28 (10) | S2—C1—Fe3 | 103.02 (13) |
Fe2—S2—Fe1 | 71.06 (2) | C1—S3—Fe3 | 61.50 (9) |
C1—S2—Fe4 | 85.30 (9) | C1—S3—Fe4 | 85.99 (9) |
Fe2—S2—Fe4 | 129.66 (3) | Fe3—S3—Fe4 | 74.01 (3) |
La chimie organométallique occupe une place importante dans la chimie moderne, due en particulier aux différentes applications qui en découlent: synthèse organique (Alper, 1976–1978), synthèse bioinorganique (Jaouen et al., 1993) et processus catalytiques (Tolman, 1972).
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 orientation différente du remplacement des carbonyles suivant le mode d'activation. Ainsi dans le complexe tétranucléaire undecacarbonyl(µ4-2-thiodithiobenzoato- κ4C,S,S',S'')(triphenyl phosphine)tetrafer (Laifa, Benali-Cherif & Berrah, 2003) le ligand PPh3 occupe une position équatoriale, alors que dans le complexe undecacarbonyl (µ4-2-thiodithiobenzoato-κ4C,S,S',S'')(trimethyl phosphite)tetrafer (Laifa, Benali-Cherif & Merazig, 2003) le ligand P(OMe)3 occupe une position axiale.
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 de la substitution de carbonyles. Partant de ce complexe et en poursuivant nos investigations sur la substitution des carbonyles par des ligands phosphines, nous avons réalisé une réaction de double substitution avec le triméthyl phosphite P(OMe)3).
Le complexe disubstitué obtenu (Fe4S3C23O16P2H22) 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 premiére substitution du carbonyle par la trimethyl phosphite a lieu spécifiquement sur le motif A symétyrique, ponté par S2 en position équatoriale par rapport à la liaison Fe1—Fe2 [Fe1—Fe2—P1 = 113.92 (3)°] et la deuxième substitution sur le motif B asymétrique est aussi en position équatoriale par rapport á la liaison Fe3—Fe4 [Fe3—Fe4—P2 = 94.48 (3)°]. Ce résultat est en accord avec la régle d'une substitution par site métallique dans les complexes polynucléaires (El Kbir et al., 1983).