supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

hy2102 scheme

Acta Cryst. (2008). E64, m217    [ doi:10.1107/S160053680706415X ]

Octacarbonyl(5-methoxy-2,3-dihydro-1H-benzimidazol-2-yl)di-[mu]3-sulfido-diiron(I)iron(II)(2 Fe-Fe)

T. Zhang, M. Wang, P. Li and L. Sun

Abstract top

The title compound, [Fe3(C8H8N2O)S2(CO)8], was prepared by the direct reaction of Fe3(CO)12 and 5-methoxy-1H-benzoimidazole-2-thiol in tetrahydrofuran. Desulfurization took place readily to form a sulfide carbonyl cluster. The molecule contains a triangle consisting of three Fe atoms capped by two S atoms above and below. There are two Fe-Fe bonds [2.6322 (5) and 2.5582 (5) Å] in the triangle; the length of the third edge [3.3987 (5) Å] is too long to represent an Fe-Fe bond.

Comment top

The chemistry of sulfide carbonyl clusters is well developed not only on account of their fascinating structural chemistry, but also because of their ability to act as electron reservoirs and potential in catalysis (Adams & Wang, 1985; Adams & Yang, 1983). Here we report the crystal structure of the title compound.

The central Fe3S2 unit in the title compound is in accord with that for the well known complex [Fe3(µ3-S)2(CO)9] (Bard et al., 1985). The molecule contains a triangle of Fe atoms capped by two S atoms above and below. There exist two Fe—Fe bonds in the molecule, that is, Fe1—Fe2 [2.6322 (5) Å] and Fe2—Fe3 [2.5582 (5) Å] bonds, while the distance between Fe1 and Fe3 [3.3987 (5) Å] is too long to form a Fe—Fe bond. The Fe1—C9 bond length [1.914 (2) Å] is similar to that for another carbene–iron complex (Benoit et al., 1982). The distances of two C9—N bonds [1.348 (3) and 1.355 (3) Å] are significantly shorter than that of the C—N single bond (1.47 Å) (Weininger & Stermitz, 1984) and longer than that of the C—N double bond (1.30 Å) (Weininger & Stermitz, 1984). The sum of the angles around the C9 atom is 359.6°, suggesting an sp2-hybridized C atom.

Related literature top

For related literature, see: Adams & Wang (1985); Adams & Yang (1983); Bard et al. (1985); Benoit et al. (1982); Weininger & Stermitz (1984).

Experimental top

Fe3(CO)12 (0.50 g, 1 mmol) was added to a solution of 5-methoxy-1H-benzoimidazole-2-thiol (0.54 g, 3 mmol) in THF (20 ml). After the solution was refluxed for 20 min, the solvent was removed under reduced pressure and the residue was chromatographed on a silica gel column with CH2Cl2/hexane (2:1 v/v) as the eluent to give the title compound as a brown solid (yield 60%, 0.36 g). Single crystals of the title compound were obtained by slow evaporation of the CH2Cl2 solution at room temperature.

Refinement top

H atoms attached to C and N atoms were positioned geometrically and refined as riding, with C—H = 0.93 (CH) and 0.97 Å (CH3), and N—H = 0.86 Å, and with Uiso(H) = 1.5Ueq(C) for methyl group and Uiso(H) = 1.2Ueq(C,N) for the others.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 30% probability level.
Octacarbonyl(5-methoxy-2,3-dihydro-1H-benzimidazol-2-yl)di-µ3– sulfido-diiron(I)iron(II)(2 Fe—Fe) top
Crystal data top
[Fe3(C8H8N2O)S2(CO)8]Z = 2
Mr = 603.91F000 = 600
Triclinic, P1Dx = 1.827 Mg m−3
Hall symbol: -P 1Mo Kα radiation
λ = 0.71073 Å
a = 9.0068 (4) ÅCell parameters from 3399 reflections
b = 11.4504 (5) Åθ = 3.6–29.3º
c = 12.5976 (6) ŵ = 2.20 mm−1
α = 112.332 (3)ºT = 273 (2) K
β = 108.728 (3)ºBlock, brown
γ = 96.229 (3)º0.25 × 0.20 × 0.10 mm
V = 1098.0 (1) Å3
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		4253 independent reflections
Radiation source: fine-focus sealed tube3584 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.019
T = 273(2) Kθmax = 26.0º
φ and ω scansθmin = 3.6º
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		h = −11→10
Tmin = 0.610, Tmax = 0.810k = −14→13
8226 measured reflectionsl = −15→15
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0345P)2 + 0.1529P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.028(Δ/σ)max = 0.001
wR(F2) = 0.070Δρmax = 0.28 e Å−3
S = 1.05Δρmin = −0.30 e Å−3
4253 reflectionsExtinction correction: none
289 parameters
Crystal data top
[Fe3(C8H8N2O)S2(CO)8]γ = 96.229 (3)º
Mr = 603.91V = 1098.0 (1) Å3
Triclinic, P1Z = 2
a = 9.0068 (4) ÅMo Kα
b = 11.4504 (5) ŵ = 2.20 mm−1
c = 12.5976 (6) ÅT = 273 (2) K
α = 112.332 (3)º0.25 × 0.20 × 0.10 mm
β = 108.728 (3)º
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		4253 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 1997)		3584 reflections with I > 2σ(I)
Tmin = 0.610, Tmax = 0.810Rint = 0.019
8226 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.028289 parameters
wR(F2) = 0.070H-atom parameters constrained
S = 1.05Δρmax = 0.28 e Å−3
4253 reflectionsΔρmin = −0.30 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe20.76196 (4)0.76148 (3)0.59336 (3)0.03973 (10)
Fe10.94423 (4)1.00067 (3)0.75013 (3)0.03945 (10)
Fe30.54802 (4)0.85600 (3)0.66569 (3)0.03970 (10)
S20.70315 (7)0.94813 (6)0.59519 (5)0.03972 (14)
S10.79595 (7)0.87177 (6)0.79494 (5)0.04141 (14)
N10.9696 (2)1.2115 (2)0.98758 (18)0.0454 (5)
H1A1.02401.17841.03330.055*
N20.8456 (2)1.24400 (19)0.83051 (17)0.0439 (5)
H2A0.80501.23560.75540.053*
C90.9253 (3)1.1612 (2)0.8629 (2)0.0406 (5)
O80.2735 (2)0.7602 (2)0.4266 (2)0.0715 (6)
O21.1025 (3)1.1243 (2)0.6350 (2)0.0833 (7)
C150.8368 (3)1.3437 (2)0.9318 (2)0.0413 (5)
C21.0438 (3)1.0765 (3)0.6799 (2)0.0530 (6)
O11.2491 (3)0.9921 (2)0.9194 (2)0.0819 (7)
C80.3784 (3)0.7992 (2)0.5209 (3)0.0475 (6)
C11.1322 (3)0.9977 (3)0.8553 (2)0.0524 (6)
C100.9171 (3)1.3231 (2)1.0340 (2)0.0443 (5)
O50.5879 (3)0.6474 (2)0.3226 (2)0.0884 (7)
C50.6572 (3)0.6905 (3)0.4274 (3)0.0555 (6)
C40.7104 (3)0.6124 (3)0.6041 (3)0.0607 (7)
O90.7147 (3)1.63452 (19)1.08295 (19)0.0690 (5)
C140.7649 (3)1.4461 (2)0.9402 (2)0.0479 (6)
H14A0.71041.45830.87030.057*
O40.6759 (3)0.5192 (2)0.6127 (3)0.0997 (9)
C130.7787 (3)1.5292 (2)1.0582 (2)0.0514 (6)
O31.0797 (3)0.7445 (3)0.5882 (3)0.1048 (9)
C30.9606 (4)0.7601 (3)0.5954 (3)0.0638 (7)
C120.8608 (4)1.5093 (3)1.1619 (3)0.0606 (7)
H12A0.86911.56731.24020.073*
O70.3939 (3)0.6703 (3)0.7320 (3)0.1099 (10)
O60.4779 (4)1.0948 (3)0.8090 (3)0.1222 (11)
C160.6157 (4)1.6512 (3)0.9793 (3)0.0694 (8)
H16A0.57821.72801.00850.104*
H16B0.52401.57600.92680.104*
H16C0.67781.66080.93240.104*
C110.9296 (4)1.4067 (3)1.1513 (2)0.0596 (7)
H11A0.98301.39371.22080.072*
C60.5036 (4)1.0008 (3)0.7545 (3)0.0670 (8)
C70.4532 (3)0.7432 (3)0.7076 (3)0.0630 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe20.03531 (18)0.03891 (18)0.0433 (2)0.00916 (14)0.01431 (15)0.01758 (15)
Fe10.03450 (18)0.04229 (19)0.03923 (19)0.00558 (14)0.01320 (14)0.01792 (15)
Fe30.03299 (17)0.0493 (2)0.04277 (19)0.01194 (14)0.01478 (15)0.02601 (16)
S20.0417 (3)0.0408 (3)0.0379 (3)0.0078 (2)0.0127 (2)0.0218 (2)
S10.0376 (3)0.0511 (3)0.0393 (3)0.0103 (2)0.0115 (2)0.0271 (3)
N10.0463 (11)0.0522 (12)0.0390 (11)0.0147 (9)0.0118 (9)0.0249 (9)
N20.0498 (12)0.0459 (11)0.0312 (10)0.0135 (9)0.0098 (9)0.0171 (9)
C90.0366 (12)0.0446 (13)0.0386 (12)0.0043 (10)0.0107 (10)0.0213 (10)
O80.0584 (12)0.0816 (14)0.0628 (13)0.0070 (10)−0.0016 (11)0.0442 (11)
O20.0897 (16)0.0868 (16)0.0683 (14)−0.0140 (12)0.0409 (13)0.0309 (12)
C150.0377 (12)0.0419 (12)0.0349 (12)0.0033 (10)0.0092 (10)0.0135 (10)
C20.0492 (15)0.0533 (15)0.0424 (14)−0.0003 (12)0.0158 (12)0.0124 (12)
O10.0495 (12)0.1139 (19)0.0762 (15)0.0262 (12)0.0098 (11)0.0468 (14)
C80.0446 (14)0.0504 (14)0.0560 (16)0.0122 (11)0.0184 (13)0.0333 (13)
C10.0425 (15)0.0593 (16)0.0506 (15)0.0078 (12)0.0174 (13)0.0217 (13)
C100.0428 (13)0.0506 (14)0.0372 (12)0.0095 (11)0.0126 (10)0.0203 (11)
O50.0985 (18)0.0868 (16)0.0450 (13)0.0029 (13)0.0138 (12)0.0118 (11)
C50.0543 (16)0.0519 (15)0.0525 (17)0.0100 (12)0.0205 (14)0.0167 (13)
C40.0521 (16)0.0481 (15)0.0701 (19)0.0088 (12)0.0095 (14)0.0274 (14)
O90.0762 (14)0.0546 (11)0.0598 (12)0.0263 (10)0.0217 (11)0.0107 (9)
C140.0471 (14)0.0452 (13)0.0421 (13)0.0096 (11)0.0092 (11)0.0176 (11)
O40.0993 (18)0.0560 (14)0.126 (2)0.0023 (13)0.0133 (16)0.0536 (14)
C130.0447 (14)0.0470 (14)0.0486 (15)0.0058 (11)0.0152 (12)0.0115 (11)
O30.0574 (14)0.115 (2)0.134 (2)0.0314 (14)0.0518 (15)0.0326 (18)
C30.0474 (16)0.0646 (18)0.074 (2)0.0155 (13)0.0261 (15)0.0226 (15)
C120.0632 (18)0.0668 (18)0.0396 (14)0.0169 (14)0.0187 (13)0.0125 (13)
O70.0737 (15)0.156 (3)0.152 (3)0.0164 (16)0.0421 (17)0.125 (2)
O60.127 (2)0.0838 (19)0.156 (3)0.0416 (17)0.096 (2)0.0157 (18)
C160.0660 (19)0.0555 (17)0.076 (2)0.0228 (14)0.0210 (17)0.0227 (15)
C110.0653 (18)0.0754 (19)0.0356 (13)0.0216 (15)0.0157 (13)0.0245 (13)
C60.0574 (17)0.070 (2)0.075 (2)0.0180 (15)0.0374 (16)0.0234 (16)
C70.0397 (14)0.095 (2)0.0701 (19)0.0154 (14)0.0162 (13)0.0568 (18)
Geometric parameters (Å, °) top
Fe2—C31.783 (3)O8—C81.135 (3)
Fe2—C41.787 (3)O2—C21.125 (3)
Fe2—C51.788 (3)C15—C101.380 (3)
Fe2—S22.2505 (7)C15—C141.386 (3)
Fe2—S12.2621 (7)O1—C11.128 (3)
Fe2—Fe32.5582 (5)C10—C111.381 (4)
Fe2—Fe12.6322 (5)O5—C51.134 (3)
Fe1—C11.797 (3)C4—O41.133 (3)
Fe1—C21.807 (3)O9—C131.366 (3)
Fe1—C91.914 (2)O9—C161.420 (3)
Fe1—S12.2294 (6)C14—C131.383 (4)
Fe1—S22.2337 (7)C14—H14A0.9300
Fe3—C81.783 (3)C13—C121.395 (4)
Fe3—C61.784 (3)O3—C31.133 (3)
Fe3—C71.801 (3)C12—C111.369 (4)
Fe3—S12.2415 (6)C12—H12A0.9300
Fe3—S22.2455 (6)O7—C71.132 (3)
N1—C91.348 (3)O6—C61.130 (4)
N1—C101.392 (3)C16—H16A0.9600
N1—H1A0.8600C16—H16B0.9600
N2—C91.355 (3)C16—H16C0.9600
N2—C151.384 (3)C11—H11A0.9300
N2—H2A0.8600
C3—Fe2—C499.51 (14)S2—Fe3—Fe255.410 (18)
C3—Fe2—C596.64 (14)Fe1—S2—Fe398.71 (2)
C4—Fe2—C594.66 (13)Fe1—S2—Fe271.89 (2)
C3—Fe2—S2110.82 (10)Fe3—S2—Fe269.362 (19)
C4—Fe2—S2149.33 (10)Fe1—S1—Fe398.96 (2)
C5—Fe2—S286.53 (9)Fe1—S1—Fe271.75 (2)
C3—Fe2—S1105.97 (10)Fe3—S1—Fe269.23 (2)
C4—Fe2—S188.38 (10)C9—N1—C10112.33 (19)
C5—Fe2—S1156.38 (9)C9—N1—H1A123.8
S2—Fe2—S179.21 (2)C10—N1—H1A123.8
C3—Fe2—Fe3156.00 (10)C9—N2—C15112.47 (19)
C4—Fe2—Fe394.73 (10)C9—N2—H2A123.8
C5—Fe2—Fe3101.37 (9)C15—N2—H2A123.8
S2—Fe2—Fe355.228 (18)N1—C9—N2103.9 (2)
S1—Fe2—Fe355.008 (18)N1—C9—Fe1129.74 (17)
C3—Fe2—Fe174.51 (10)N2—C9—Fe1126.01 (17)
C4—Fe2—Fe1135.67 (10)C10—C15—N2105.7 (2)
C5—Fe2—Fe1129.47 (9)C10—C15—C14122.9 (2)
S2—Fe2—Fe153.760 (18)N2—C15—C14131.4 (2)
S1—Fe2—Fe153.551 (18)O2—C2—Fe1178.4 (3)
Fe3—Fe2—Fe181.794 (15)O8—C8—Fe3177.5 (3)
C1—Fe1—C293.34 (12)O1—C1—Fe1178.0 (3)
C1—Fe1—C996.89 (11)C15—C10—C11120.2 (2)
C2—Fe1—C994.73 (11)C15—C10—N1105.6 (2)
C1—Fe1—S192.65 (8)C11—C10—N1134.2 (2)
C2—Fe1—S1167.53 (8)O5—C5—Fe2178.2 (3)
C9—Fe1—S195.40 (7)O4—C4—Fe2178.4 (3)
C1—Fe1—S2165.00 (9)C13—O9—C16117.3 (2)
C2—Fe1—S291.31 (8)C13—C14—C15116.2 (2)
C9—Fe1—S296.92 (7)C13—C14—H14A121.9
S1—Fe1—S280.26 (2)C15—C14—H14A121.9
C1—Fe1—Fe2110.82 (9)O9—C13—C14123.8 (2)
C2—Fe1—Fe2112.86 (8)O9—C13—C12115.1 (2)
C9—Fe1—Fe2138.68 (7)C14—C13—C12121.1 (2)
S1—Fe1—Fe254.701 (19)O3—C3—Fe2172.2 (3)
S2—Fe1—Fe254.352 (18)C11—C12—C13121.7 (2)
C8—Fe3—C699.45 (14)C11—C12—H12A119.1
C8—Fe3—C791.77 (12)C13—C12—H12A119.1
C6—Fe3—C799.30 (15)O9—C16—H16A109.5
C8—Fe3—S1156.98 (9)O9—C16—H16B109.5
C6—Fe3—S1102.43 (11)H16A—C16—H16B109.5
C7—Fe3—S191.72 (9)O9—C16—H16C109.5
C8—Fe3—S290.45 (8)H16A—C16—H16C109.5
C6—Fe3—S297.38 (10)H16B—C16—H16C109.5
C7—Fe3—S2162.57 (10)C12—C11—C10117.8 (2)
S1—Fe3—S279.75 (2)C12—C11—H11A121.1
C8—Fe3—Fe2101.57 (9)C10—C11—H11A121.1
C6—Fe3—Fe2145.32 (10)O6—C6—Fe3177.5 (3)
C7—Fe3—Fe2107.26 (10)O7—C7—Fe3178.6 (3)
S1—Fe3—Fe255.765 (19)
Table 1
Selected geometric parameters (Å, °) top
Fe2—S22.2505 (7)Fe1—S12.2294 (6)
Fe2—S12.2621 (7)Fe1—S22.2337 (7)
Fe2—Fe32.5582 (5)Fe3—S12.2415 (6)
Fe2—Fe12.6322 (5)Fe3—S22.2455 (6)
Fe1—C91.914 (2)
C9—Fe1—Fe2138.68 (7)Fe3—S2—Fe269.362 (19)
C6—Fe3—Fe2145.32 (10)Fe1—S1—Fe398.96 (2)
Fe1—S2—Fe398.71 (2)Fe1—S1—Fe271.75 (2)
Fe1—S2—Fe271.89 (2)Fe3—S1—Fe269.23 (2)
Acknowledgements top

We are grateful to the Chinese National Natural Science Foundation (Grant Nos. 20471013 and 20633020), the Swedish Energy Agency, the Swedish Research Council and K & A Wallenberg Foundation for financial supports of this work.

references
References top

Adams, R. D. & Wang, S. (1985). Organometallics, 5, 1272–1274.

Adams, R. D. & Yang, L.-W. (1983). J. Am. Chem. Soc. 105, 235–240.

Bard, A. J., Cowley, A. H., Leland, J. K., Thomas, G. J. N., Norman, N. C., Jutzi, P., Morley, C. P. & Schlüter, E. (1985). J. Chem. Soc. Dalton Trans. pp. 1303–1307.

Benoit, A., Marouille, J. L. & Patin, C. (1982). J. Organomet. Chem. 233, C51–C54.

Bruker (1997). SMART (Version 5.611), SADABS (Version 2.03) and SHELXTL (Version 5.10). Bruker AXS Inc., Madison, Wisconsin, USA.

Bruker (2001). SAINT-Plus. Bruker AXS Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Weininger, S. J. & Stermitz, F. R. (1984). Organic Chemistry. USA: Academic Press.