metal-organic compounds
Heptacarbonylbis(μ-propane-1,3-dithiolato)triiron(I,II)(2 Fe—Fe)
aState Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Fuzhou, Fujian 350002, People's Republic of China
*Correspondence e-mail: ccn@fjirsm.ac.cn
The trinuclear title compound, [Fe3(C3H6S2)2(CO)7], is a mixed-valent FeI/FeII complex and crystallizes with two molecules of similar configuration in the The three Fe atoms in each molecule display a bent arrangement [Fe—Fe—Fe = 156.22 (4) and 157.06 (3)°]. Both outer FeI atoms are six-coordinated in a distorted ocahedral coordination geometry defined by the bridging FeII atom, three carbonyl C atoms and two bridging S atoms. The of the central FeII atom is seven and includes bonding to the two outer FeI atoms, four bridging S atoms and one carbonyl C atom. The resulting might be described as a highly distorted monocapped trigonal prism. In the crystal packing, the molecules exhibit a chain-like arrangement parallel to [100] and [001], and the resulting layers are stacked along [010]. The cohesion of the structure is dominated by van der Waals interactions.
CCDC reference: 989211
Related literature
For models of the active sites of Fe—Fe hydrogenases, see: Tard et al. (2005); Best et al. (2007). For the structures of similar trinuclear mixed-valence iron complexes, see: Winter et al. (1982); Ghosh et al. (2011).
Experimental
Crystal data
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Data collection: CrystalClear (Rigaku, 2007); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
CCDC reference: 989211
10.1107/S1600536814004619/wm5007sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814004619/wm5007Isup2.hkl
The title compound, [FeI/II3(C3H6S2)2(CO)7] (I), was prepared as a model compound for the active sites of Fe—Fe hydrogenases and structurally characterized by single-crystal X-ray diffraction. Such models have been reported for similar other compounds, e.g. Fe4[H3CC(CH2S)3]2(CO)8 (Tard et al., 2005) and [Fe4(S(CH2)2S)2(CO)2(CO)8]22- (Best et al., 2007).
Compound (I) crystallizes with two independent trinuclear iron molecules in the ≈ 2.56 Å), by three terminal carbonyl C atoms and by two bridging S atoms (Fe—S: ≈ 2.26 Å), leading to an overall distorted octahedral coordination environment. The central FeII atom is seven-coordinated. It is bound to the two lateral Fe atoms, to four bridging S atoms (Fe—S: ≈ 2.23-2.27 Å) and to one carbonyl group (Fe—C: ≈ 1.76 Å), completing a highly distorted monocapped trigonal-prismatic coordination environment.
Formally, the three iron atoms in each molecule exhibit a mixed-valence, with the central Fe atom in +II and the two lateral Fe atoms in +I. Both molecules have a similar configuration and similar bond lengths and angles. The three Fe atoms display a slightly bent Fe3 core with Fe—Fe—Fe angles of 156.22 (4)° and 157.06 (3)°), respectively (Fig. 1). The outer FeI atoms are each six-coordinated by the central FeII atom (Fe—Fe:In the crystal, the molecules are arranged in chains extending parallel to [100] and [001], resulting in a layer-like arrangement. These layers are stacked along [010] (Fig. 2). The main forces keeping the structure stabilized are van der Waals interactions.
Structures of similar trinuclear mixed-valence iron complexes have been reported by Winter et al. (1982) and Ghosh et al. (2011).
Reactions were carried out under an atmosphere of purified nitrogen, using standard Schlenk techniques. 5 g of Fe3(CO)12 were suspended in 200 mL of THF followed by the addition of two equivalents of 1,3-propanedithiol. The reaction mixture was stirred at 343 k until its color changed from deep green to dark red. The reaction mixture was allowed to cool to room temperature and was filtered. The volume was reduced under vacuum to ca. 5 mL, and passed through a 25 X 3.0 cm column of silica gel, eluting with hexane. The eluting CH2Cl2 solution of a second run was collected and evaporated to dryness under vacuum. Red crystals of (I) were obtained from a hexane/CH2Cl2 solution at 253 K.
Data collection: CrystalClear (Rigaku, 2007); cell
CrystalClear (Rigaku, 2007); data reduction: CrystalClear (Rigaku, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2010).[Fe3(C3H6S2)2(CO)7] | F(000) = 2304 |
Mr = 576.02 | Dx = 1.881 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.710747 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 13590 reflections |
a = 10.251 (3) Å | θ = 2.1–27.4° |
b = 12.838 (4) Å | µ = 2.55 mm−1 |
c = 30.915 (9) Å | T = 293 K |
V = 4068 (2) Å3 | Prism, red |
Z = 8 | 0.25 × 0.20 × 0.12 mm |
Rigaku Saturn724+ CCD diffractometer | 9231 independent reflections |
Graphite Monochromator monochromator | 8082 reflections with I > 2σ(I) |
Detector resolution: 28.5714 pixels mm-1 | Rint = 0.071 |
CCD_Profile_fitting scans | θmax = 27.4°, θmin = 2.5° |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | h = −8→13 |
Tmin = 0.592, Tmax = 1.000 | k = −16→16 |
35336 measured reflections | l = −40→40 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.056 | w = 1/[σ2(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.86 | (Δ/σ)max = 0.001 |
9231 reflections | Δρmax = 0.43 e Å−3 |
488 parameters | Δρmin = −0.56 e Å−3 |
0 restraints | Absolute structure: Flack (1983), 4075 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.016 (13) |
[Fe3(C3H6S2)2(CO)7] | V = 4068 (2) Å3 |
Mr = 576.02 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.251 (3) Å | µ = 2.55 mm−1 |
b = 12.838 (4) Å | T = 293 K |
c = 30.915 (9) Å | 0.25 × 0.20 × 0.12 mm |
Rigaku Saturn724+ CCD diffractometer | 9231 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2007) | 8082 reflections with I > 2σ(I) |
Tmin = 0.592, Tmax = 1.000 | Rint = 0.071 |
35336 measured reflections |
R[F2 > 2σ(F2)] = 0.043 | H-atom parameters constrained |
wR(F2) = 0.056 | Δρmax = 0.43 e Å−3 |
S = 0.86 | Δρmin = −0.56 e Å−3 |
9231 reflections | Absolute structure: Flack (1983), 4075 Friedel pairs |
488 parameters | Absolute structure parameter: 0.016 (13) |
0 restraints |
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 | 1.04804 (6) | 0.49655 (6) | 0.03335 (2) | 0.04003 (16) | |
Fe2 | 0.81125 (6) | 0.50119 (5) | 0.059552 (18) | 0.03290 (14) | |
Fe3 | 0.61279 (7) | 0.57503 (6) | 0.09894 (2) | 0.04215 (17) | |
Fe4 | 0.36509 (6) | 0.91038 (5) | 0.19958 (2) | 0.03942 (16) | |
Fe5 | 0.12719 (6) | 0.97257 (5) | 0.198539 (19) | 0.03369 (15) | |
Fe6 | −0.07197 (6) | 1.07640 (5) | 0.17247 (2) | 0.03880 (16) | |
S1 | 0.98615 (11) | 0.53021 (9) | 0.10260 (3) | 0.0396 (3) | |
S2 | 0.90097 (12) | 0.62123 (9) | 0.01479 (4) | 0.0416 (3) | |
S3 | 0.70965 (11) | 0.42116 (10) | 0.11404 (4) | 0.0434 (3) | |
S4 | 0.61473 (11) | 0.51916 (9) | 0.02945 (3) | 0.0414 (3) | |
S5 | 0.22266 (12) | 0.87810 (10) | 0.14501 (4) | 0.0425 (3) | |
S6 | 0.30258 (12) | 1.07940 (10) | 0.19239 (4) | 0.0463 (3) | |
S7 | 0.02210 (12) | 1.09168 (9) | 0.23814 (4) | 0.0413 (3) | |
S8 | −0.06917 (11) | 0.90355 (9) | 0.18638 (3) | 0.0376 (3) | |
C1 | 1.1229 (5) | 0.3756 (4) | 0.05168 (16) | 0.0531 (14) | |
C2 | 1.1914 (5) | 0.5763 (5) | 0.03410 (15) | 0.0612 (15) | |
C3 | 1.0602 (5) | 0.4602 (4) | −0.02280 (15) | 0.0521 (13) | |
C4 | 0.5998 (6) | 0.7046 (5) | 0.07693 (17) | 0.0632 (17) | |
C5 | 0.6824 (5) | 0.6222 (4) | 0.14889 (16) | 0.0583 (15) | |
C6 | 0.4492 (5) | 0.5602 (5) | 0.11754 (16) | 0.0666 (17) | |
C7 | 0.5117 (5) | 0.9168 (4) | 0.16823 (15) | 0.0513 (13) | |
C8 | 0.3729 (6) | 0.7714 (4) | 0.20949 (15) | 0.0533 (14) | |
C9 | 0.4340 (5) | 0.9398 (4) | 0.25218 (16) | 0.0561 (14) | |
C10 | −0.0930 (5) | 1.0443 (4) | 0.11620 (15) | 0.0564 (15) | |
C11 | 0.0016 (5) | 1.1998 (4) | 0.16003 (16) | 0.0530 (14) | |
C12 | −0.2357 (5) | 1.1221 (4) | 0.18135 (15) | 0.0509 (14) | |
C21 | 0.9519 (5) | 0.7426 (3) | 0.04054 (15) | 0.0595 (15) | |
H21A | 1.0420 | 0.7560 | 0.0327 | 0.071* | |
H21B | 0.8997 | 0.7989 | 0.0288 | 0.071* | |
C22 | 0.9411 (6) | 0.7454 (4) | 0.08884 (15) | 0.0635 (17) | |
H22A | 0.8498 | 0.7369 | 0.0964 | 0.076* | |
H22B | 0.9674 | 0.8142 | 0.0985 | 0.076* | |
C23 | 1.0183 (5) | 0.6664 (4) | 0.11395 (15) | 0.0554 (14) | |
H23A | 1.0026 | 0.6783 | 0.1445 | 0.066* | |
H23B | 1.1102 | 0.6794 | 0.1087 | 0.066* | |
C31 | 0.6108 (5) | 0.3124 (4) | 0.09543 (17) | 0.0590 (15) | |
H31A | 0.6675 | 0.2641 | 0.0803 | 0.071* | |
H31B | 0.5770 | 0.2765 | 0.1207 | 0.071* | |
C32 | 0.4959 (5) | 0.3380 (4) | 0.06570 (16) | 0.0618 (16) | |
H32A | 0.4511 | 0.2736 | 0.0587 | 0.074* | |
H32B | 0.4351 | 0.3817 | 0.0814 | 0.074* | |
C33 | 0.5323 (5) | 0.3929 (4) | 0.02356 (15) | 0.0549 (14) | |
H33A | 0.4533 | 0.4034 | 0.0068 | 0.066* | |
H33B | 0.5886 | 0.3471 | 0.0070 | 0.066* | |
C51 | 0.2710 (5) | 0.9530 (4) | 0.09738 (14) | 0.0581 (16) | |
H51A | 0.3612 | 0.9366 | 0.0907 | 0.070* | |
H51B | 0.2184 | 0.9303 | 0.0731 | 0.070* | |
C52 | 0.2581 (5) | 1.0704 (4) | 0.10154 (15) | 0.0610 (15) | |
H52A | 0.2823 | 1.1016 | 0.0741 | 0.073* | |
H52B | 0.1670 | 1.0869 | 0.1066 | 0.073* | |
C53 | 0.3386 (5) | 1.1211 (4) | 0.13688 (16) | 0.0601 (15) | |
H53A | 0.3261 | 1.1959 | 0.1352 | 0.072* | |
H53B | 0.4299 | 1.1072 | 0.1311 | 0.072* | |
C71 | −0.0791 (4) | 1.0318 (4) | 0.28009 (12) | 0.0501 (13) | |
H71A | −0.0229 | 0.9900 | 0.2984 | 0.060* | |
H71B | −0.1148 | 1.0871 | 0.2979 | 0.060* | |
C72 | −0.1902 (4) | 0.9643 (4) | 0.26522 (13) | 0.0462 (12) | |
H72A | −0.2515 | 1.0075 | 0.2494 | 0.055* | |
H72B | −0.2351 | 0.9378 | 0.2906 | 0.055* | |
C73 | −0.1534 (4) | 0.8733 (3) | 0.23698 (14) | 0.0472 (12) | |
H73A | −0.2324 | 0.8352 | 0.2300 | 0.057* | |
H73B | −0.0982 | 0.8271 | 0.2537 | 0.057* | |
C91 | 0.8475 (4) | 0.3835 (4) | 0.03267 (15) | 0.0481 (13) | |
C92 | 0.1597 (4) | 0.8936 (4) | 0.24367 (14) | 0.0435 (12) | |
O1 | 1.1711 (4) | 0.3008 (3) | 0.06250 (13) | 0.0823 (14) | |
O2 | 1.2807 (4) | 0.6289 (4) | 0.03471 (13) | 0.0925 (16) | |
O3 | 1.0733 (4) | 0.4380 (3) | −0.05810 (10) | 0.0705 (11) | |
O4 | 0.5945 (5) | 0.7865 (3) | 0.06323 (13) | 0.0987 (17) | |
O5 | 0.7256 (4) | 0.6517 (3) | 0.18024 (11) | 0.0864 (15) | |
O6 | 0.3438 (4) | 0.5517 (4) | 0.13040 (12) | 0.0974 (17) | |
O7 | 0.6055 (3) | 0.9183 (3) | 0.14762 (11) | 0.0738 (12) | |
O8 | 0.3816 (5) | 0.6846 (3) | 0.21508 (13) | 0.0889 (14) | |
O9 | 0.4785 (4) | 0.9553 (3) | 0.28507 (11) | 0.0871 (15) | |
O10 | −0.1054 (4) | 1.0259 (3) | 0.08036 (10) | 0.0889 (14) | |
O11 | 0.0512 (4) | 1.2781 (3) | 0.15233 (12) | 0.0840 (14) | |
O12 | −0.3387 (4) | 1.1547 (3) | 0.18505 (12) | 0.0740 (13) | |
O91 | 0.8444 (4) | 0.3005 (3) | 0.01739 (12) | 0.0741 (12) | |
O92 | 0.1563 (3) | 0.8449 (3) | 0.27565 (11) | 0.0635 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0352 (4) | 0.0464 (4) | 0.0385 (3) | −0.0028 (3) | −0.0006 (3) | 0.0037 (3) |
Fe2 | 0.0332 (3) | 0.0332 (4) | 0.0323 (3) | −0.0016 (3) | −0.0031 (3) | −0.0013 (3) |
Fe3 | 0.0407 (4) | 0.0513 (4) | 0.0345 (3) | 0.0075 (4) | −0.0042 (3) | −0.0054 (3) |
Fe4 | 0.0354 (4) | 0.0387 (4) | 0.0441 (4) | −0.0018 (3) | −0.0002 (3) | −0.0029 (3) |
Fe5 | 0.0325 (3) | 0.0334 (4) | 0.0351 (3) | −0.0030 (3) | 0.0006 (3) | −0.0001 (3) |
Fe6 | 0.0416 (4) | 0.0383 (4) | 0.0364 (3) | 0.0038 (3) | −0.0007 (3) | −0.0005 (3) |
S1 | 0.0433 (7) | 0.0418 (7) | 0.0338 (6) | −0.0068 (5) | −0.0075 (5) | 0.0024 (5) |
S2 | 0.0483 (8) | 0.0385 (7) | 0.0380 (6) | −0.0040 (6) | −0.0090 (5) | 0.0068 (5) |
S3 | 0.0407 (7) | 0.0484 (8) | 0.0410 (6) | −0.0056 (6) | −0.0036 (5) | 0.0082 (6) |
S4 | 0.0405 (7) | 0.0478 (8) | 0.0359 (6) | 0.0011 (6) | −0.0081 (5) | −0.0030 (5) |
S5 | 0.0394 (7) | 0.0469 (8) | 0.0411 (6) | −0.0073 (6) | 0.0033 (5) | −0.0071 (5) |
S6 | 0.0440 (7) | 0.0348 (7) | 0.0602 (8) | −0.0082 (6) | 0.0065 (6) | −0.0024 (6) |
S7 | 0.0463 (7) | 0.0380 (7) | 0.0397 (6) | −0.0006 (6) | −0.0011 (5) | −0.0070 (5) |
S8 | 0.0366 (6) | 0.0348 (6) | 0.0414 (6) | −0.0041 (5) | 0.0013 (5) | −0.0050 (5) |
C1 | 0.045 (3) | 0.063 (4) | 0.051 (3) | 0.000 (3) | 0.007 (2) | 0.002 (3) |
C2 | 0.055 (3) | 0.085 (4) | 0.044 (3) | −0.012 (3) | −0.003 (3) | 0.017 (3) |
C3 | 0.045 (3) | 0.059 (4) | 0.053 (3) | 0.001 (3) | −0.001 (2) | 0.006 (3) |
C4 | 0.071 (4) | 0.066 (4) | 0.053 (3) | 0.021 (3) | −0.017 (3) | −0.015 (3) |
C5 | 0.064 (4) | 0.065 (4) | 0.045 (3) | 0.006 (3) | 0.005 (3) | −0.002 (3) |
C6 | 0.057 (4) | 0.097 (5) | 0.046 (3) | 0.019 (4) | −0.006 (3) | −0.013 (3) |
C7 | 0.045 (3) | 0.056 (3) | 0.054 (3) | −0.004 (3) | −0.006 (2) | −0.005 (3) |
C8 | 0.063 (4) | 0.045 (3) | 0.052 (3) | 0.001 (3) | 0.007 (3) | 0.000 (2) |
C9 | 0.045 (3) | 0.070 (4) | 0.053 (3) | −0.002 (3) | 0.006 (2) | −0.008 (3) |
C10 | 0.060 (4) | 0.059 (4) | 0.051 (3) | 0.010 (3) | 0.001 (3) | 0.008 (3) |
C11 | 0.059 (4) | 0.048 (3) | 0.052 (3) | 0.006 (3) | 0.006 (3) | −0.002 (3) |
C12 | 0.055 (4) | 0.047 (3) | 0.050 (3) | 0.004 (3) | −0.004 (3) | 0.007 (2) |
C21 | 0.083 (4) | 0.039 (3) | 0.057 (3) | −0.003 (3) | −0.018 (3) | 0.005 (2) |
C22 | 0.088 (5) | 0.035 (3) | 0.067 (4) | −0.002 (3) | −0.026 (3) | −0.005 (3) |
C23 | 0.072 (4) | 0.044 (3) | 0.050 (3) | −0.012 (3) | −0.014 (3) | −0.001 (2) |
C31 | 0.050 (3) | 0.053 (4) | 0.075 (4) | −0.013 (3) | −0.007 (3) | 0.014 (3) |
C32 | 0.047 (4) | 0.072 (4) | 0.066 (4) | −0.021 (3) | −0.008 (3) | −0.005 (3) |
C33 | 0.047 (3) | 0.063 (4) | 0.055 (3) | −0.014 (3) | −0.010 (2) | −0.017 (3) |
C51 | 0.054 (3) | 0.084 (5) | 0.037 (3) | −0.007 (3) | 0.008 (2) | −0.001 (3) |
C52 | 0.057 (4) | 0.074 (4) | 0.052 (3) | 0.007 (3) | 0.018 (3) | 0.018 (3) |
C53 | 0.054 (4) | 0.046 (3) | 0.080 (4) | −0.007 (3) | 0.015 (3) | 0.018 (3) |
C71 | 0.057 (3) | 0.057 (3) | 0.036 (2) | 0.003 (3) | 0.008 (2) | −0.007 (2) |
C72 | 0.043 (3) | 0.051 (3) | 0.044 (3) | 0.004 (2) | 0.012 (2) | −0.002 (2) |
C73 | 0.043 (3) | 0.048 (3) | 0.051 (3) | −0.004 (2) | 0.007 (2) | 0.003 (2) |
C91 | 0.038 (3) | 0.052 (3) | 0.055 (3) | −0.001 (2) | 0.006 (2) | −0.006 (3) |
C92 | 0.035 (3) | 0.048 (3) | 0.048 (3) | 0.001 (2) | −0.001 (2) | 0.000 (2) |
O1 | 0.078 (3) | 0.078 (3) | 0.091 (3) | 0.036 (3) | 0.006 (2) | 0.020 (2) |
O2 | 0.061 (3) | 0.122 (4) | 0.094 (3) | −0.044 (3) | −0.005 (2) | 0.033 (3) |
O3 | 0.080 (3) | 0.085 (3) | 0.047 (2) | 0.005 (2) | 0.004 (2) | −0.011 (2) |
O4 | 0.159 (5) | 0.052 (3) | 0.085 (3) | 0.039 (3) | −0.041 (3) | −0.003 (2) |
O5 | 0.112 (4) | 0.099 (4) | 0.049 (2) | −0.017 (3) | −0.024 (2) | −0.019 (2) |
O6 | 0.053 (3) | 0.168 (5) | 0.071 (3) | 0.011 (3) | 0.009 (2) | −0.010 (3) |
O7 | 0.046 (2) | 0.100 (3) | 0.076 (3) | −0.009 (2) | 0.015 (2) | −0.011 (2) |
O8 | 0.125 (4) | 0.046 (3) | 0.095 (3) | 0.011 (3) | 0.013 (3) | 0.009 (2) |
O9 | 0.068 (3) | 0.138 (4) | 0.055 (2) | −0.015 (3) | −0.010 (2) | −0.023 (3) |
O10 | 0.118 (4) | 0.109 (4) | 0.040 (2) | 0.014 (3) | −0.010 (2) | −0.003 (2) |
O11 | 0.114 (4) | 0.049 (3) | 0.088 (3) | −0.007 (3) | 0.031 (3) | 0.011 (2) |
O12 | 0.054 (3) | 0.087 (3) | 0.081 (3) | 0.020 (2) | 0.000 (2) | 0.004 (2) |
O91 | 0.067 (3) | 0.053 (3) | 0.103 (3) | −0.007 (2) | 0.009 (2) | −0.037 (2) |
O92 | 0.052 (2) | 0.079 (3) | 0.060 (2) | 0.005 (2) | 0.0071 (19) | 0.030 (2) |
Fe1—C2 | 1.791 (5) | C3—O3 | 1.136 (5) |
Fe1—C3 | 1.802 (5) | C4—O4 | 1.135 (6) |
Fe1—C1 | 1.823 (5) | C5—O5 | 1.131 (5) |
Fe1—S2 | 2.2724 (14) | C6—O6 | 1.156 (6) |
Fe1—S1 | 2.2743 (14) | C7—O7 | 1.154 (5) |
Fe1—Fe2 | 2.5596 (11) | C8—O8 | 1.131 (5) |
Fe2—C91 | 1.764 (5) | C9—O9 | 1.132 (5) |
Fe2—S4 | 2.2310 (13) | C10—O10 | 1.140 (5) |
Fe2—S3 | 2.2311 (13) | C11—O11 | 1.152 (6) |
Fe2—S1 | 2.2637 (13) | C12—O12 | 1.142 (6) |
Fe2—S2 | 2.2662 (13) | C21—C22 | 1.498 (6) |
Fe2—Fe3 | 2.5534 (10) | C21—H21A | 0.9700 |
Fe3—C6 | 1.783 (6) | C21—H21B | 0.9700 |
Fe3—C4 | 1.802 (6) | C22—C23 | 1.503 (6) |
Fe3—C5 | 1.806 (5) | C22—H22A | 0.9700 |
Fe3—S3 | 2.2596 (15) | C22—H22B | 0.9700 |
Fe3—S4 | 2.2648 (13) | C23—H23A | 0.9700 |
Fe4—C7 | 1.790 (5) | C23—H23B | 0.9700 |
Fe4—C8 | 1.812 (5) | C31—C32 | 1.529 (6) |
Fe4—C9 | 1.813 (5) | C31—H31A | 0.9700 |
Fe4—S5 | 2.2692 (14) | C31—H31B | 0.9700 |
Fe4—S6 | 2.2734 (15) | C32—C33 | 1.528 (6) |
Fe4—Fe5 | 2.5662 (11) | C32—H32A | 0.9700 |
Fe5—C92 | 1.757 (4) | C32—H32B | 0.9700 |
Fe5—S8 | 2.2310 (13) | C33—H33A | 0.9700 |
Fe5—S7 | 2.2355 (13) | C33—H33B | 0.9700 |
Fe5—S6 | 2.2693 (14) | C51—C52 | 1.519 (6) |
Fe5—S5 | 2.2731 (14) | C51—H51A | 0.9700 |
Fe5—Fe6 | 2.5679 (10) | C51—H51B | 0.9700 |
Fe6—C11 | 1.796 (5) | C52—C53 | 1.516 (6) |
Fe6—C12 | 1.799 (5) | C52—H52A | 0.9700 |
Fe6—C10 | 1.801 (5) | C52—H52B | 0.9700 |
Fe6—S7 | 2.2562 (14) | C53—H53A | 0.9700 |
Fe6—S8 | 2.2604 (14) | C53—H53B | 0.9700 |
S1—C23 | 1.814 (5) | C71—C72 | 1.503 (6) |
S2—C21 | 1.826 (4) | C71—H71A | 0.9700 |
S3—C31 | 1.818 (5) | C71—H71B | 0.9700 |
S4—C33 | 1.836 (4) | C72—C73 | 1.506 (5) |
S5—C51 | 1.827 (4) | C72—H72A | 0.9700 |
S6—C53 | 1.835 (5) | C72—H72B | 0.9700 |
S7—C71 | 1.830 (4) | C73—H73A | 0.9700 |
S8—C73 | 1.829 (4) | C73—H73B | 0.9700 |
C1—O1 | 1.131 (6) | C91—O91 | 1.165 (5) |
C2—O2 | 1.138 (6) | C92—O92 | 1.170 (5) |
C2—Fe1—C3 | 96.0 (2) | C21—S2—Fe1 | 107.53 (17) |
C2—Fe1—C1 | 97.9 (2) | Fe2—S2—Fe1 | 68.66 (4) |
C3—Fe1—C1 | 92.8 (2) | C31—S3—Fe2 | 112.00 (17) |
C2—Fe1—S2 | 98.35 (19) | C31—S3—Fe3 | 111.15 (17) |
C3—Fe1—S2 | 89.15 (16) | Fe2—S3—Fe3 | 69.30 (4) |
C1—Fe1—S2 | 163.32 (17) | C33—S4—Fe2 | 111.44 (16) |
C2—Fe1—S1 | 96.21 (17) | C33—S4—Fe3 | 111.68 (16) |
C3—Fe1—S1 | 167.26 (16) | Fe2—S4—Fe3 | 69.21 (4) |
C1—Fe1—S1 | 89.23 (16) | C51—S5—Fe4 | 109.19 (17) |
S2—Fe1—S1 | 85.34 (5) | C51—S5—Fe5 | 115.02 (18) |
C2—Fe1—Fe2 | 139.53 (19) | Fe4—S5—Fe5 | 68.80 (4) |
C3—Fe1—Fe2 | 112.12 (16) | C53—S6—Fe5 | 114.44 (16) |
C1—Fe1—Fe2 | 108.69 (16) | C53—S6—Fe4 | 108.24 (17) |
S2—Fe1—Fe2 | 55.56 (4) | Fe5—S6—Fe4 | 68.79 (5) |
S1—Fe1—Fe2 | 55.47 (3) | C71—S7—Fe5 | 111.96 (16) |
C91—Fe2—S4 | 94.73 (16) | C71—S7—Fe6 | 111.03 (15) |
C91—Fe2—S3 | 93.42 (16) | Fe5—S7—Fe6 | 69.74 (4) |
S4—Fe2—S3 | 86.62 (5) | C73—S8—Fe5 | 111.49 (16) |
C91—Fe2—S1 | 104.54 (16) | C73—S8—Fe6 | 111.43 (15) |
S4—Fe2—S1 | 160.62 (5) | Fe5—S8—Fe6 | 69.74 (4) |
S3—Fe2—S1 | 90.09 (5) | O1—C1—Fe1 | 178.7 (5) |
C91—Fe2—S2 | 102.08 (16) | O2—C2—Fe1 | 178.4 (6) |
S4—Fe2—S2 | 92.37 (5) | O3—C3—Fe1 | 177.1 (5) |
S3—Fe2—S2 | 164.50 (6) | O4—C4—Fe3 | 178.4 (6) |
S1—Fe2—S2 | 85.73 (5) | O5—C5—Fe3 | 179.7 (6) |
C91—Fe2—Fe3 | 135.28 (15) | O6—C6—Fe3 | 178.5 (5) |
S4—Fe2—Fe3 | 56.02 (4) | O7—C7—Fe4 | 178.2 (5) |
S3—Fe2—Fe3 | 55.88 (4) | O8—C8—Fe4 | 177.8 (6) |
S1—Fe2—Fe3 | 106.83 (4) | O9—C9—Fe4 | 178.0 (6) |
S2—Fe2—Fe3 | 111.23 (5) | O10—C10—Fe6 | 178.6 (5) |
C91—Fe2—Fe1 | 68.35 (15) | O11—C11—Fe6 | 178.5 (6) |
S4—Fe2—Fe1 | 136.61 (4) | O12—C12—Fe6 | 176.2 (5) |
S3—Fe2—Fe1 | 132.14 (4) | C22—C21—S2 | 115.7 (3) |
S1—Fe2—Fe1 | 55.86 (4) | C22—C21—H21A | 108.3 |
S2—Fe2—Fe1 | 55.79 (4) | S2—C21—H21A | 108.4 |
Fe3—Fe2—Fe1 | 156.22 (4) | C22—C21—H21B | 108.3 |
C6—Fe3—C4 | 98.7 (3) | S2—C21—H21B | 108.3 |
C6—Fe3—C5 | 97.6 (2) | H21A—C21—H21B | 107.4 |
C4—Fe3—C5 | 92.4 (2) | C21—C22—C23 | 117.4 (5) |
C6—Fe3—S3 | 104.7 (2) | C21—C22—H22A | 108.0 |
C4—Fe3—S3 | 156.6 (2) | C23—C22—H22A | 108.0 |
C5—Fe3—S3 | 86.73 (17) | C21—C22—H22B | 108.0 |
C6—Fe3—S4 | 106.28 (17) | C23—C22—H22B | 108.0 |
C4—Fe3—S4 | 86.26 (16) | H22A—C22—H22B | 107.2 |
C5—Fe3—S4 | 156.04 (18) | C22—C23—S1 | 117.0 (3) |
S3—Fe3—S4 | 85.15 (5) | C22—C23—H23A | 108.0 |
C6—Fe3—Fe2 | 149.7 (2) | S1—C23—H23A | 108.0 |
C4—Fe3—Fe2 | 102.81 (19) | C22—C23—H23B | 108.0 |
C5—Fe3—Fe2 | 102.55 (17) | S1—C23—H23B | 108.0 |
S3—Fe3—Fe2 | 54.82 (4) | H23A—C23—H23B | 107.3 |
S4—Fe3—Fe2 | 54.77 (4) | C32—C31—S3 | 117.1 (4) |
C7—Fe4—C8 | 95.7 (2) | C32—C31—H31A | 108.0 |
C7—Fe4—C9 | 98.6 (2) | S3—C31—H31A | 108.0 |
C8—Fe4—C9 | 92.1 (2) | C32—C31—H31B | 108.0 |
C7—Fe4—S5 | 98.40 (16) | S3—C31—H31B | 108.0 |
C8—Fe4—S5 | 88.53 (17) | H31A—C31—H31B | 107.3 |
C9—Fe4—S5 | 162.87 (16) | C33—C32—C31 | 115.0 (4) |
C7—Fe4—S6 | 98.05 (18) | C33—C32—H32A | 108.5 |
C8—Fe4—S6 | 165.65 (19) | C31—C32—H32A | 108.5 |
C9—Fe4—S6 | 89.92 (18) | C33—C32—H32B | 108.5 |
S5—Fe4—S6 | 85.43 (5) | C31—C32—H32B | 108.5 |
C7—Fe4—Fe5 | 140.97 (16) | H32A—C32—H32B | 107.5 |
C8—Fe4—Fe5 | 110.52 (19) | C32—C33—S4 | 115.8 (3) |
C9—Fe4—Fe5 | 108.46 (16) | C32—C33—H33A | 108.3 |
S5—Fe4—Fe5 | 55.67 (4) | S4—C33—H33A | 108.3 |
S6—Fe4—Fe5 | 55.53 (4) | C32—C33—H33B | 108.3 |
C92—Fe5—S8 | 94.36 (15) | S4—C33—H33B | 108.3 |
C92—Fe5—S7 | 92.93 (16) | H33A—C33—H33B | 107.4 |
S8—Fe5—S7 | 85.94 (5) | C52—C51—S5 | 115.5 (4) |
C92—Fe5—S6 | 105.36 (16) | C52—C51—H51A | 108.4 |
S8—Fe5—S6 | 160.16 (5) | S5—C51—H51A | 108.4 |
S7—Fe5—S6 | 90.81 (5) | C52—C51—H51B | 108.4 |
C92—Fe5—S5 | 100.88 (16) | S5—C51—H51B | 108.4 |
S8—Fe5—S5 | 93.09 (5) | H51A—C51—H51B | 107.5 |
S7—Fe5—S5 | 166.19 (5) | C53—C52—C51 | 116.1 (5) |
S6—Fe5—S5 | 85.43 (5) | C53—C52—H52A | 108.3 |
C92—Fe5—Fe4 | 68.29 (15) | C51—C52—H52A | 108.3 |
S8—Fe5—Fe4 | 137.38 (5) | C53—C52—H52B | 108.3 |
S7—Fe5—Fe4 | 131.59 (4) | C51—C52—H52B | 108.3 |
S6—Fe5—Fe4 | 55.68 (4) | H52A—C52—H52B | 107.4 |
S5—Fe5—Fe4 | 55.53 (4) | C52—C53—S6 | 116.1 (3) |
C92—Fe5—Fe6 | 134.41 (15) | C52—C53—H53A | 108.3 |
S8—Fe5—Fe6 | 55.67 (4) | S6—C53—H53A | 108.3 |
S7—Fe5—Fe6 | 55.51 (4) | C52—C53—H53B | 108.3 |
S6—Fe5—Fe6 | 106.85 (5) | S6—C53—H53B | 108.3 |
S5—Fe5—Fe6 | 113.00 (4) | H53A—C53—H53B | 107.4 |
Fe4—Fe5—Fe6 | 157.06 (3) | C72—C71—S7 | 117.1 (3) |
C11—Fe6—C12 | 97.9 (2) | C72—C71—H71A | 108.0 |
C11—Fe6—C10 | 92.6 (2) | S7—C71—H71A | 108.0 |
C12—Fe6—C10 | 96.4 (2) | C72—C71—H71B | 108.0 |
C11—Fe6—S7 | 86.36 (17) | S7—C71—H71B | 108.0 |
C12—Fe6—S7 | 103.47 (16) | H71A—C71—H71B | 107.3 |
C10—Fe6—S7 | 160.10 (17) | C71—C72—C73 | 115.8 (4) |
C11—Fe6—S8 | 154.33 (17) | C71—C72—H72A | 108.3 |
C12—Fe6—S8 | 107.63 (17) | C73—C72—H72A | 108.3 |
C10—Fe6—S8 | 87.73 (17) | C71—C72—H72B | 108.3 |
S7—Fe6—S8 | 84.77 (5) | C73—C72—H72B | 108.3 |
C11—Fe6—Fe5 | 101.04 (17) | H72A—C72—H72B | 107.4 |
C12—Fe6—Fe5 | 149.66 (15) | C72—C73—S8 | 116.7 (3) |
C10—Fe6—Fe5 | 106.21 (16) | C72—C73—H73A | 108.1 |
S7—Fe6—Fe5 | 54.75 (4) | S8—C73—H73A | 108.1 |
S8—Fe6—Fe5 | 54.59 (4) | C72—C73—H73B | 108.1 |
C23—S1—Fe2 | 114.61 (16) | S8—C73—H73B | 108.1 |
C23—S1—Fe1 | 108.34 (17) | H73A—C73—H73B | 107.3 |
Fe2—S1—Fe1 | 68.67 (4) | O91—C91—Fe2 | 165.4 (4) |
C21—S2—Fe2 | 115.47 (16) | O92—C92—Fe5 | 166.8 (4) |
Experimental details
Crystal data | |
Chemical formula | [Fe3(C3H6S2)2(CO)7] |
Mr | 576.02 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 10.251 (3), 12.838 (4), 30.915 (9) |
V (Å3) | 4068 (2) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.55 |
Crystal size (mm) | 0.25 × 0.20 × 0.12 |
Data collection | |
Diffractometer | Rigaku Saturn724+ CCD diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2007) |
Tmin, Tmax | 0.592, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 35336, 9231, 8082 |
Rint | 0.071 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.043, 0.056, 0.86 |
No. of reflections | 9231 |
No. of parameters | 488 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.43, −0.56 |
Absolute structure | Flack (1983), 4075 Friedel pairs |
Absolute structure parameter | 0.016 (13) |
Computer programs: CrystalClear (Rigaku, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2010).
Acknowledgements
We thank NNSF of China (Nos. 21173219 and 21203195) and the NSF of Fujian Province (2011 J01063) for supporting this work.
References
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