supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers buy article online

Acta Cryst. (2007). E63, m1997    [ doi:10.1107/S1600536807025469 ]

[[mu]-2-(9-Anthrylmethyl)-2-azapropane-1,3-dithiolato-[kappa]4S:S']bis[tricarbonyliron(I)]

S. Gao and X.-J. Peng

Abstract top

The title compound, [Fe2(C17H15NS2)(CO)6], has been prepared as an azadithiolatoiron model for the active site of iron-only hydrogenase. Each Fe atom is coordinated by two S atoms and three carbonyl groups in a distorted square-pyramidal geometry and the Fe-Fe bond length [2.5040 (8) Å] agrees with values found in other model structures.

Comment top

Hydrogenases are enzymes which catalyze the reduction of protons in numerous microorganisms (Cammack, 1999; Evans & Pickett, 2003). The active site of iron-only hydrogenases, [Fe]H2ases, resembles many well known iron–sulfur–carbonyl complexes (Reihlen et al., 1928; Seyferth et al., 1980). As a novel hexacarbonyl iron–sulfur complex, the title compound, (I), was prepared to mimic structurally the active site of [Fe]H2ases. We report here the crystal structure of (I).

In agreement with the other reported models (Ott et al., 2004; Wang et al., 2005), each Fe atom is coordinated in a distorted square-pyramidal geometry and the 2Fe2S unit is in a butterfly framework. The sum of the C—N—C angles around the N atom is 350°, roughly consistent with an sp3-hybridization of the N atom. The anthrylmethyl moiety is located over the Fe2 side. The angle of C6—Fe2—Fe1 [156.0 (1)°] is enlarged by 9° compared with that of C1—Fe1—Fe2 [146.9 (1)°], thus indicating an interaction between the anthrylmethyl moiety and the Fe2(CO)3 unit. The length of Fe—Fe bond [2.5040 (8) Å] also agrees with those found in the other model structures.

Related literature top

For general background, see: Cammack (1999); Evans & Pickett (2003); Reihlen et al. (1928); Seyferth et al. (1980). For related structures, see: Ott et al. (2004); Wang et al. (2005). For ligand synthesis, see: Lawrence et al. (2004).

Experimental top

The starting compound N,N'-bis(chloromethyl)-9-anthrylmethylamine was prepared in 62% yield from 9-anthrylmethylamine (Lawrence et al., 2004). LiEt3BH (1 M solution in THF, 2.9 ml, 2.9 mmol) was dropped into the degassed solution of (µ-S2)Fe2(CO)6 (0.500 g, 1.45 mmol) in dry THF (30 ml) by syringe at 195 K over 30 min. N,N'-bis(chloromethyl)-9-anthrylmethylamine (0.882 g, 2.9 mmol) was added to the resulting dark green solution, causing an immediate change in color to red. After stirring for 2 h at 195 K, the reaction mixture was allowed to warm up to room temperature. The solvent was removed in vacuo and the resulting dark red solid was purified by column chromatography (silica, 20% dichloromethane in hexane as eluent). The product was obtained as a red solid (yield 58%, 0.485 g). Single crystals of (I) for X-ray analysis were obtained from hexane–dichloromethane (10:1 v/v,) solution by slow evaporation at room temperature.

Refinement top

H atoms attached to C atoms were positioned geometrically and refined as riding atoms, with C—H = 0.93 Å(CH) and 0.97 Å(CH2) and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); 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, 2001); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
[µ-2-(9-Anthrylmethyl)-2-azapropane-1,3-dithiolato- κ4S:S']bis[tricarbonyliron(I)] top
Crystal data top
[Fe2(C17H15NS2)(CO)6]F000 = 2336
Mr = 577.18Dx = 1.631 Mg m−3
Orthorhombic, PbcnMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2n2abCell parameters from 3797 reflections
a = 15.234 (6) Åθ = 2.3–21.5º
b = 11.945 (4) ŵ = 1.45 mm−1
c = 25.840 (9) ÅT = 273 (2) K
V = 4702 (3) Å3Block, red
Z = 80.40 × 0.22 × 0.19 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		5291 independent reflections
Radiation source: fine-focus sealed tube3449 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
T = 273(2) Kθmax = 27.3º
φ and ω scansθmin = 2.1º
Absorption correction: multi-scan
(SAINT-Plus; Bruker, 2001)		h = −19→18
Tmin = 0.598, Tmax = 0.775k = −15→15
26672 measured reflectionsl = −33→25
Refinement top
Refinement on F2307 parameters
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.037  w = 1/[σ2(Fo2) + (0.0308P)2 + 1.1601P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max = 0.001
S = 1.01Δρmax = 0.30 e Å−3
5291 reflectionsΔρmin = −0.28 e Å−3
Crystal data top
[Fe2(C17H15NS2)(CO)6]V = 4702 (3) Å3
Mr = 577.18Z = 8
Orthorhombic, PbcnMo Kα
a = 15.234 (6) ŵ = 1.45 mm−1
b = 11.945 (4) ÅT = 273 (2) K
c = 25.840 (9) Å0.40 × 0.22 × 0.19 mm
Data collection top
Bruker SMART APEXII CCD area-detector
diffractometer		5291 independent reflections
Absorption correction: multi-scan
(SAINT-Plus; Bruker, 2001)		3449 reflections with I > 2σ(I)
Tmin = 0.598, Tmax = 0.775Rint = 0.053
26672 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037307 parameters
wR(F2) = 0.085H-atom parameters constrained
S = 1.01Δρmax = 0.30 e Å−3
5291 reflectionsΔρmin = −0.28 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Fe10.01243 (3)0.34007 (3)0.401622 (15)0.04372 (12)
Fe2−0.10799 (3)0.22027 (3)0.437450 (15)0.04836 (13)
S1−0.12743 (5)0.34232 (6)0.37191 (3)0.04503 (18)
S20.00238 (5)0.15340 (6)0.38759 (3)0.04378 (17)
O10.10661 (18)0.4136 (2)0.30884 (10)0.0954 (9)
O2−0.01662 (18)0.55954 (19)0.44916 (9)0.0829 (8)
O30.16070 (19)0.2935 (2)0.47039 (11)0.1016 (9)
O4−0.1836 (2)0.3828 (2)0.50913 (11)0.1051 (10)
O5−0.0141 (2)0.1204 (3)0.52462 (11)0.1190 (11)
O6−0.2595 (2)0.0692 (2)0.43504 (10)0.1103 (11)
N1−0.10819 (14)0.16234 (18)0.29960 (8)0.0427 (5)
C10.0710 (2)0.3850 (3)0.34544 (13)0.0590 (8)
C2−0.0057 (2)0.4742 (3)0.43081 (11)0.0559 (8)
C30.1030 (2)0.3116 (3)0.44377 (13)0.0625 (9)
C4−0.1556 (2)0.3200 (3)0.48055 (13)0.0675 (9)
C5−0.0514 (3)0.1581 (3)0.49060 (14)0.0747 (10)
C6−0.2004 (3)0.1270 (3)0.43469 (12)0.0690 (10)
C7−0.13032 (19)0.2773 (2)0.30616 (10)0.0493 (7)
H7A−0.18920.28750.29260.059*
H7B−0.09130.32040.28420.059*
C8−0.02359 (17)0.1320 (2)0.31746 (10)0.0428 (6)
H8A0.01910.17370.29740.051*
H8B−0.01490.05330.30960.051*
C9−0.17766 (17)0.0783 (2)0.30591 (11)0.0481 (7)
H9A−0.23380.11140.29700.058*
H9B−0.18020.05500.34180.058*
C10−0.16135 (16)−0.0230 (2)0.27191 (11)0.0407 (6)
C11−0.13325 (17)−0.1252 (2)0.29368 (11)0.0433 (7)
C12−0.1195 (2)−0.1424 (3)0.34751 (12)0.0585 (8)
H12A−0.1262−0.08250.37020.070*
C13−0.0968 (2)−0.2441 (3)0.36658 (13)0.0716 (10)
H13A−0.0886−0.25290.40200.086*
C14−0.0855 (2)−0.3366 (3)0.33342 (14)0.0677 (9)
H14A−0.0710−0.40610.34710.081*
C15−0.09537 (19)−0.3247 (2)0.28227 (13)0.0550 (8)
H15A−0.0869−0.38620.26080.066*
C16−0.11872 (16)−0.2194 (2)0.26002 (11)0.0413 (6)
C17−0.12973 (18)−0.2074 (2)0.20710 (11)0.0471 (7)
H17A−0.1179−0.26810.18560.057*
C18−0.15776 (17)−0.1080 (2)0.18520 (11)0.0434 (7)
C19−0.1719 (2)−0.0981 (3)0.13090 (12)0.0561 (8)
H19A−0.1597−0.15870.10950.067*
C20−0.2025 (2)−0.0029 (3)0.11016 (12)0.0638 (9)
H20A−0.21260.00140.07470.077*
C21−0.2193 (2)0.0906 (3)0.14192 (12)0.0592 (8)
H21A−0.23980.15650.12720.071*
C22−0.20588 (18)0.0855 (2)0.19360 (12)0.0500 (7)
H22A−0.21710.14850.21370.060*
C23−0.17492 (16)−0.0139 (2)0.21809 (10)0.0400 (6)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Fe10.0490 (2)0.0460 (2)0.0361 (2)−0.00432 (19)−0.00347 (17)−0.00198 (18)
Fe20.0580 (3)0.0470 (2)0.0400 (2)−0.0015 (2)0.01166 (19)−0.00189 (19)
S10.0487 (4)0.0398 (4)0.0466 (4)0.0050 (3)−0.0019 (3)−0.0058 (3)
S20.0448 (4)0.0455 (4)0.0410 (4)0.0065 (3)−0.0015 (3)−0.0014 (3)
O10.101 (2)0.124 (2)0.0615 (16)−0.0508 (18)0.0168 (14)−0.0018 (16)
O20.136 (2)0.0519 (14)0.0603 (15)0.0105 (15)−0.0311 (14)−0.0096 (12)
O30.092 (2)0.118 (2)0.095 (2)0.0179 (17)−0.0492 (17)−0.0143 (18)
O40.137 (3)0.0893 (19)0.089 (2)0.0102 (18)0.0498 (18)−0.0313 (16)
O50.172 (3)0.127 (3)0.0581 (17)0.020 (2)−0.0165 (19)0.0233 (18)
O60.118 (2)0.117 (2)0.096 (2)−0.065 (2)0.0450 (18)−0.0324 (17)
N10.0401 (13)0.0431 (13)0.0448 (13)0.0011 (11)−0.0019 (10)−0.0083 (11)
C10.061 (2)0.067 (2)0.0486 (19)−0.0214 (17)−0.0052 (16)−0.0085 (16)
C20.075 (2)0.0543 (19)0.0388 (17)−0.0056 (17)−0.0162 (15)0.0053 (15)
C30.063 (2)0.066 (2)0.059 (2)−0.0007 (17)−0.0106 (17)−0.0135 (17)
C40.080 (2)0.064 (2)0.059 (2)−0.0060 (18)0.0219 (18)−0.0072 (18)
C50.109 (3)0.070 (2)0.045 (2)0.004 (2)0.009 (2)0.0062 (18)
C60.085 (3)0.070 (2)0.052 (2)−0.016 (2)0.0289 (18)−0.0154 (17)
C70.0556 (19)0.0486 (17)0.0438 (16)0.0038 (14)−0.0088 (13)−0.0057 (14)
C80.0374 (15)0.0492 (16)0.0417 (16)−0.0015 (12)0.0037 (12)−0.0101 (13)
C90.0369 (16)0.0540 (18)0.0534 (18)−0.0015 (13)0.0023 (13)−0.0116 (14)
C100.0298 (14)0.0458 (16)0.0467 (16)−0.0057 (12)0.0010 (12)−0.0065 (13)
C110.0353 (15)0.0473 (17)0.0473 (17)−0.0058 (12)−0.0001 (12)−0.0029 (13)
C120.065 (2)0.065 (2)0.0460 (18)−0.0023 (17)−0.0070 (15)−0.0011 (16)
C130.087 (3)0.078 (3)0.050 (2)−0.005 (2)−0.0120 (18)0.0109 (19)
C140.069 (2)0.058 (2)0.077 (3)0.0024 (17)−0.0117 (18)0.022 (2)
C150.0475 (18)0.0456 (17)0.072 (2)−0.0027 (14)−0.0038 (15)0.0011 (16)
C160.0286 (14)0.0425 (15)0.0528 (17)−0.0027 (12)−0.0010 (12)−0.0010 (13)
C170.0456 (17)0.0421 (16)0.0536 (18)−0.0043 (13)0.0045 (13)−0.0089 (14)
C180.0364 (15)0.0482 (17)0.0455 (17)−0.0087 (13)−0.0005 (12)−0.0039 (14)
C190.061 (2)0.0592 (19)0.0481 (18)−0.0080 (16)−0.0021 (15)−0.0047 (16)
C200.065 (2)0.080 (2)0.0460 (19)−0.0072 (18)−0.0031 (15)0.0066 (18)
C210.0521 (19)0.063 (2)0.063 (2)0.0017 (16)−0.0031 (15)0.0135 (17)
C220.0406 (17)0.0497 (17)0.060 (2)0.0007 (13)−0.0001 (14)0.0006 (15)
C230.0286 (14)0.0448 (16)0.0468 (16)−0.0062 (12)−0.0011 (11)−0.0003 (13)
Geometric parameters (Å, °) top
Fe1—C11.786 (4)C9—H9A0.9700
Fe1—C31.791 (3)C9—H9B0.9700
Fe1—C21.792 (3)C10—C231.410 (4)
Fe1—S22.2643 (11)C10—C111.410 (4)
Fe1—S12.2649 (11)C11—C121.422 (4)
Fe1—Fe22.5040 (8)C11—C161.440 (4)
Fe2—C51.783 (4)C12—C131.356 (4)
Fe2—C41.785 (3)C12—H12A0.9300
Fe2—C61.797 (4)C13—C141.409 (5)
Fe2—S12.2542 (10)C13—H13A0.9300
Fe2—S22.2639 (10)C14—C151.338 (4)
S1—C71.869 (3)C14—H14A0.9300
S2—C81.872 (3)C15—C161.428 (4)
O1—C11.143 (4)C15—H15A0.9300
O2—C21.137 (3)C16—C171.385 (4)
O3—C31.137 (4)C17—C181.383 (4)
O4—C41.136 (3)C17—H17A0.9300
O5—C51.140 (4)C18—C191.424 (4)
O6—C61.135 (4)C18—C231.433 (4)
N1—C81.416 (3)C19—C201.340 (4)
N1—C71.424 (3)C19—H19A0.9300
N1—C91.468 (3)C20—C211.410 (4)
C7—H7A0.9700C20—H20A0.9300
C7—H7B0.9700C21—C221.352 (4)
C8—H8A0.9700C21—H21A0.9300
C8—H8B0.9700C22—C231.426 (4)
C9—C101.516 (3)C22—H22A0.9300
C1—Fe1—C399.59 (16)S2—C8—H8A107.8
C1—Fe1—C298.65 (15)N1—C8—H8B107.8
C3—Fe1—C291.86 (14)S2—C8—H8B107.8
C1—Fe1—S2101.50 (11)H8A—C8—H8B107.1
C3—Fe1—S287.84 (11)N1—C9—C10111.3 (2)
C2—Fe1—S2159.62 (10)N1—C9—H9A109.4
C1—Fe1—S1100.98 (11)C10—C9—H9A109.4
C3—Fe1—S1158.98 (12)N1—C9—H9B109.4
C2—Fe1—S189.28 (10)C10—C9—H9B109.4
S2—Fe1—S183.90 (3)H9A—C9—H9B108.0
C1—Fe1—Fe2146.91 (10)C23—C10—C11120.3 (2)
C3—Fe1—Fe2103.36 (12)C23—C10—C9119.1 (2)
C2—Fe1—Fe2104.04 (11)C11—C10—C9120.6 (2)
S2—Fe1—Fe256.42 (3)C10—C11—C12124.1 (3)
S1—Fe1—Fe256.15 (3)C10—C11—C16118.8 (2)
C5—Fe2—C489.64 (17)C12—C11—C16117.1 (3)
C5—Fe2—C698.69 (18)C13—C12—C11121.5 (3)
C4—Fe2—C696.92 (15)C13—C12—H12A119.2
C5—Fe2—S1155.70 (13)C11—C12—H12A119.2
C4—Fe2—S189.06 (12)C12—C13—C14120.8 (3)
C6—Fe2—S1105.56 (12)C12—C13—H13A119.6
C5—Fe2—S286.13 (12)C14—C13—H13A119.6
C4—Fe2—S2153.17 (11)C15—C14—C13120.2 (3)
C6—Fe2—S2109.91 (10)C15—C14—H14A119.9
S1—Fe2—S284.16 (3)C13—C14—H14A119.9
C5—Fe2—Fe199.71 (13)C14—C15—C16121.3 (3)
C4—Fe2—Fe198.44 (11)C14—C15—H15A119.3
C6—Fe2—Fe1156.02 (10)C16—C15—H15A119.3
S1—Fe2—Fe156.56 (3)C17—C16—C15121.2 (3)
S2—Fe2—Fe156.44 (3)C17—C16—C11119.8 (2)
C7—S1—Fe2114.67 (9)C15—C16—C11118.9 (3)
C7—S1—Fe1108.99 (10)C18—C17—C16122.0 (3)
Fe2—S1—Fe167.30 (3)C18—C17—H17A119.0
C8—S2—Fe2116.24 (9)C16—C17—H17A119.0
C8—S2—Fe1107.69 (9)C17—C18—C19121.4 (3)
Fe2—S2—Fe167.14 (3)C17—C18—C23119.1 (2)
C8—N1—C7115.1 (2)C19—C18—C23119.4 (3)
C8—N1—C9116.4 (2)C20—C19—C18121.1 (3)
C7—N1—C9118.4 (2)C20—C19—H19A119.4
O1—C1—Fe1178.4 (3)C18—C19—H19A119.4
O2—C2—Fe1179.5 (4)C19—C20—C21120.2 (3)
O3—C3—Fe1179.8 (4)C19—C20—H20A119.9
O4—C4—Fe2177.7 (4)C21—C20—H20A119.9
O5—C5—Fe2178.5 (4)C22—C21—C20120.8 (3)
O6—C6—Fe2177.1 (3)C22—C21—H21A119.6
N1—C7—S1120.22 (19)C20—C21—H21A119.6
N1—C7—H7A107.3C21—C22—C23121.7 (3)
S1—C7—H7A107.3C21—C22—H22A119.2
N1—C7—H7B107.3C23—C22—H22A119.2
S1—C7—H7B107.3C10—C23—C22123.4 (2)
H7A—C7—H7B106.9C10—C23—C18119.9 (2)
N1—C8—S2118.21 (18)C22—C23—C18116.8 (2)
N1—C8—H8A107.8
Table 1
Selected geometric parameters (Å, °) top
Fe1—C11.786 (4)Fe2—C51.783 (4)
Fe1—C31.791 (3)Fe2—C41.785 (3)
Fe1—C21.792 (3)Fe2—C61.797 (4)
Fe1—S22.2643 (11)Fe2—S12.2542 (10)
Fe1—S12.2649 (11)Fe2—S22.2639 (10)
Fe1—Fe22.5040 (8)
C1—Fe1—Fe2146.91 (10)C6—Fe2—Fe1156.02 (10)
Acknowledgements top

This work was supported by the Ministry of Education of China and the National Natural Science Foundation of China (Nos. 20128005, 20376010 and 20472012).

references
References top

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

Cammack, R. (1999). Nature, 297, 214–215.

Evans, D. J. & Pickett, C. J. (2003). Chem. Soc. Rev. 32, 268–275.

Lawrence, J. D., Li, H. & Rauchfuss, T. B. (2004). Chem. Commun. pp. 1482–1483.

Ott, S., Kritikos, M., Åkermark, B., Sun, L. C. & Lomoth, R. (2004). Angew. Chem. Int. Ed. 43, 1006–1009.

Reihlen, H. J., Friedolsheim, A. & Oswald, W. (1928). Liebigs Ann. Chem. 465, 72–96.

Seyferth, D., Henderson, R. S. & Song, L. C. (1980). J. Organomet. Chem. 192, C1–C5.

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

Wang, F. J., Wang, M., Liu, X. Y., Jin, K., Dong, W. B., Li, G. H., Åkermark, B. & Sun, L. C. (2005). Chem. Commun. pp. 3221–3223.