Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807025469/hy2063sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807025469/hy2063Isup2.hkl |
CCDC reference: 654823
Key indicators
- Single-crystal X-ray study
- T = 273 K
- Mean (C-C) = 0.004 Å
- R factor = 0.037
- wR factor = 0.085
- Data-to-parameter ratio = 17.2
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.98 PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe1 - C1 .. 6.30 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe1 - C2 .. 8.01 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe1 - C3 .. 6.21 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe2 - C4 .. 5.72 su PLAT232_ALERT_2_C Hirshfeld Test Diff (M-X) Fe2 - C6 .. 5.11 su PLAT410_ALERT_2_C Short Intra H...H Contact H9B .. H12A .. 1.98 Ang.
Alert level G PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe1 (3) 3.75 PLAT794_ALERT_5_G Check Predicted Bond Valency for Fe2 (3) 3.78
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 7 ALERT level C = Check and explain 2 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 6 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 2 ALERT type 5 Informative message, check
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).
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.
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).
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.
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).
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.
Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. |
[Fe2(C17H15NS2)(CO)6] | F(000) = 2336 |
Mr = 577.18 | Dx = 1.631 Mg m−3 |
Orthorhombic, Pbcn | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2n2ab | Cell parameters from 3797 reflections |
a = 15.234 (6) Å | θ = 2.3–21.5° |
b = 11.945 (4) Å | µ = 1.45 mm−1 |
c = 25.840 (9) Å | T = 273 K |
V = 4702 (3) Å3 | Block, red |
Z = 8 | 0.40 × 0.22 × 0.19 mm |
Bruker SMART APEXII CCD area-detector diffractometer | 5291 independent reflections |
Radiation source: fine-focus sealed tube | 3449 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.053 |
φ and ω scans | θmax = 27.3°, θmin = 2.1° |
Absorption correction: multi-scan (SAINT-Plus; Bruker, 2001) | h = −19→18 |
Tmin = 0.598, Tmax = 0.775 | k = −15→15 |
26672 measured reflections | l = −33→25 |
Refinement on F2 | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.085 | w = 1/[σ2(Fo2) + (0.0308P)2 + 1.1601P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
5291 reflections | Δρmax = 0.30 e Å−3 |
307 parameters | Δρmin = −0.28 e Å−3 |
[Fe2(C17H15NS2)(CO)6] | V = 4702 (3) Å3 |
Mr = 577.18 | Z = 8 |
Orthorhombic, Pbcn | Mo Kα radiation |
a = 15.234 (6) Å | µ = 1.45 mm−1 |
b = 11.945 (4) Å | T = 273 K |
c = 25.840 (9) Å | 0.40 × 0.22 × 0.19 mm |
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 = 0.775 | Rint = 0.053 |
26672 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.085 | H-atom parameters constrained |
S = 1.01 | Δρmax = 0.30 e Å−3 |
5291 reflections | Δρmin = −0.28 e Å−3 |
307 parameters |
x | y | z | Uiso*/Ueq | ||
Fe1 | 0.01243 (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) | |
S2 | 0.00238 (5) | 0.15340 (6) | 0.38759 (3) | 0.04378 (17) | |
O1 | 0.10661 (18) | 0.4136 (2) | 0.30884 (10) | 0.0954 (9) | |
O2 | −0.01662 (18) | 0.55954 (19) | 0.44916 (9) | 0.0829 (8) | |
O3 | 0.16070 (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) | |
C1 | 0.0710 (2) | 0.3850 (3) | 0.34544 (13) | 0.0590 (8) | |
C2 | −0.0057 (2) | 0.4742 (3) | 0.43081 (11) | 0.0559 (8) | |
C3 | 0.1030 (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 | −0.1892 | 0.2875 | 0.2926 | 0.059* | |
H7B | −0.0913 | 0.3204 | 0.2842 | 0.059* | |
C8 | −0.02359 (17) | 0.1320 (2) | 0.31746 (10) | 0.0428 (6) | |
H8A | 0.0191 | 0.1737 | 0.2974 | 0.051* | |
H8B | −0.0149 | 0.0533 | 0.3096 | 0.051* | |
C9 | −0.17766 (17) | 0.0783 (2) | 0.30591 (11) | 0.0481 (7) | |
H9A | −0.2338 | 0.1114 | 0.2970 | 0.058* | |
H9B | −0.1802 | 0.0550 | 0.3418 | 0.058* | |
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 | −0.0825 | 0.3702 | 0.070* | |
C13 | −0.0968 (2) | −0.2441 (3) | 0.36658 (13) | 0.0716 (10) | |
H13A | −0.0886 | −0.2529 | 0.4020 | 0.086* | |
C14 | −0.0855 (2) | −0.3366 (3) | 0.33342 (14) | 0.0677 (9) | |
H14A | −0.0710 | −0.4061 | 0.3471 | 0.081* | |
C15 | −0.09537 (19) | −0.3247 (2) | 0.28227 (13) | 0.0550 (8) | |
H15A | −0.0869 | −0.3862 | 0.2608 | 0.066* | |
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 | −0.2681 | 0.1856 | 0.057* | |
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 | −0.1587 | 0.1095 | 0.067* | |
C20 | −0.2025 (2) | −0.0029 (3) | 0.11016 (12) | 0.0638 (9) | |
H20A | −0.2126 | 0.0014 | 0.0747 | 0.077* | |
C21 | −0.2193 (2) | 0.0906 (3) | 0.14192 (12) | 0.0592 (8) | |
H21A | −0.2398 | 0.1565 | 0.1272 | 0.071* | |
C22 | −0.20588 (18) | 0.0855 (2) | 0.19360 (12) | 0.0500 (7) | |
H22A | −0.2171 | 0.1485 | 0.2137 | 0.060* | |
C23 | −0.17492 (16) | −0.0139 (2) | 0.21809 (10) | 0.0400 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe1 | 0.0490 (2) | 0.0460 (2) | 0.0361 (2) | −0.00432 (19) | −0.00347 (17) | −0.00198 (18) |
Fe2 | 0.0580 (3) | 0.0470 (2) | 0.0400 (2) | −0.0015 (2) | 0.01166 (19) | −0.00189 (19) |
S1 | 0.0487 (4) | 0.0398 (4) | 0.0466 (4) | 0.0050 (3) | −0.0019 (3) | −0.0058 (3) |
S2 | 0.0448 (4) | 0.0455 (4) | 0.0410 (4) | 0.0065 (3) | −0.0015 (3) | −0.0014 (3) |
O1 | 0.101 (2) | 0.124 (2) | 0.0615 (16) | −0.0508 (18) | 0.0168 (14) | −0.0018 (16) |
O2 | 0.136 (2) | 0.0519 (14) | 0.0603 (15) | 0.0105 (15) | −0.0311 (14) | −0.0096 (12) |
O3 | 0.092 (2) | 0.118 (2) | 0.095 (2) | 0.0179 (17) | −0.0492 (17) | −0.0143 (18) |
O4 | 0.137 (3) | 0.0893 (19) | 0.089 (2) | 0.0102 (18) | 0.0498 (18) | −0.0313 (16) |
O5 | 0.172 (3) | 0.127 (3) | 0.0581 (17) | 0.020 (2) | −0.0165 (19) | 0.0233 (18) |
O6 | 0.118 (2) | 0.117 (2) | 0.096 (2) | −0.065 (2) | 0.0450 (18) | −0.0324 (17) |
N1 | 0.0401 (13) | 0.0431 (13) | 0.0448 (13) | 0.0011 (11) | −0.0019 (10) | −0.0083 (11) |
C1 | 0.061 (2) | 0.067 (2) | 0.0486 (19) | −0.0214 (17) | −0.0052 (16) | −0.0085 (16) |
C2 | 0.075 (2) | 0.0543 (19) | 0.0388 (17) | −0.0056 (17) | −0.0162 (15) | 0.0053 (15) |
C3 | 0.063 (2) | 0.066 (2) | 0.059 (2) | −0.0007 (17) | −0.0106 (17) | −0.0135 (17) |
C4 | 0.080 (2) | 0.064 (2) | 0.059 (2) | −0.0060 (18) | 0.0219 (18) | −0.0072 (18) |
C5 | 0.109 (3) | 0.070 (2) | 0.045 (2) | 0.004 (2) | 0.009 (2) | 0.0062 (18) |
C6 | 0.085 (3) | 0.070 (2) | 0.052 (2) | −0.016 (2) | 0.0289 (18) | −0.0154 (17) |
C7 | 0.0556 (19) | 0.0486 (17) | 0.0438 (16) | 0.0038 (14) | −0.0088 (13) | −0.0057 (14) |
C8 | 0.0374 (15) | 0.0492 (16) | 0.0417 (16) | −0.0015 (12) | 0.0037 (12) | −0.0101 (13) |
C9 | 0.0369 (16) | 0.0540 (18) | 0.0534 (18) | −0.0015 (13) | 0.0023 (13) | −0.0116 (14) |
C10 | 0.0298 (14) | 0.0458 (16) | 0.0467 (16) | −0.0057 (12) | 0.0010 (12) | −0.0065 (13) |
C11 | 0.0353 (15) | 0.0473 (17) | 0.0473 (17) | −0.0058 (12) | −0.0001 (12) | −0.0029 (13) |
C12 | 0.065 (2) | 0.065 (2) | 0.0460 (18) | −0.0023 (17) | −0.0070 (15) | −0.0011 (16) |
C13 | 0.087 (3) | 0.078 (3) | 0.050 (2) | −0.005 (2) | −0.0120 (18) | 0.0109 (19) |
C14 | 0.069 (2) | 0.058 (2) | 0.077 (3) | 0.0024 (17) | −0.0117 (18) | 0.022 (2) |
C15 | 0.0475 (18) | 0.0456 (17) | 0.072 (2) | −0.0027 (14) | −0.0038 (15) | 0.0011 (16) |
C16 | 0.0286 (14) | 0.0425 (15) | 0.0528 (17) | −0.0027 (12) | −0.0010 (12) | −0.0010 (13) |
C17 | 0.0456 (17) | 0.0421 (16) | 0.0536 (18) | −0.0043 (13) | 0.0045 (13) | −0.0089 (14) |
C18 | 0.0364 (15) | 0.0482 (17) | 0.0455 (17) | −0.0087 (13) | −0.0005 (12) | −0.0039 (14) |
C19 | 0.061 (2) | 0.0592 (19) | 0.0481 (18) | −0.0080 (16) | −0.0021 (15) | −0.0047 (16) |
C20 | 0.065 (2) | 0.080 (2) | 0.0460 (19) | −0.0072 (18) | −0.0031 (15) | 0.0066 (18) |
C21 | 0.0521 (19) | 0.063 (2) | 0.063 (2) | 0.0017 (16) | −0.0031 (15) | 0.0135 (17) |
C22 | 0.0406 (17) | 0.0497 (17) | 0.060 (2) | 0.0007 (13) | −0.0001 (14) | 0.0006 (15) |
C23 | 0.0286 (14) | 0.0448 (16) | 0.0468 (16) | −0.0062 (12) | −0.0011 (11) | −0.0003 (13) |
Fe1—C1 | 1.786 (4) | C9—H9A | 0.9700 |
Fe1—C3 | 1.791 (3) | C9—H9B | 0.9700 |
Fe1—C2 | 1.792 (3) | C10—C23 | 1.410 (4) |
Fe1—S2 | 2.2643 (11) | C10—C11 | 1.410 (4) |
Fe1—S1 | 2.2649 (11) | C11—C12 | 1.422 (4) |
Fe1—Fe2 | 2.5040 (8) | C11—C16 | 1.440 (4) |
Fe2—C5 | 1.783 (4) | C12—C13 | 1.356 (4) |
Fe2—C4 | 1.785 (3) | C12—H12A | 0.9300 |
Fe2—C6 | 1.797 (4) | C13—C14 | 1.409 (5) |
Fe2—S1 | 2.2542 (10) | C13—H13A | 0.9300 |
Fe2—S2 | 2.2639 (10) | C14—C15 | 1.338 (4) |
S1—C7 | 1.869 (3) | C14—H14A | 0.9300 |
S2—C8 | 1.872 (3) | C15—C16 | 1.428 (4) |
O1—C1 | 1.143 (4) | C15—H15A | 0.9300 |
O2—C2 | 1.137 (3) | C16—C17 | 1.385 (4) |
O3—C3 | 1.137 (4) | C17—C18 | 1.383 (4) |
O4—C4 | 1.136 (3) | C17—H17A | 0.9300 |
O5—C5 | 1.140 (4) | C18—C19 | 1.424 (4) |
O6—C6 | 1.135 (4) | C18—C23 | 1.433 (4) |
N1—C8 | 1.416 (3) | C19—C20 | 1.340 (4) |
N1—C7 | 1.424 (3) | C19—H19A | 0.9300 |
N1—C9 | 1.468 (3) | C20—C21 | 1.410 (4) |
C7—H7A | 0.9700 | C20—H20A | 0.9300 |
C7—H7B | 0.9700 | C21—C22 | 1.352 (4) |
C8—H8A | 0.9700 | C21—H21A | 0.9300 |
C8—H8B | 0.9700 | C22—C23 | 1.426 (4) |
C9—C10 | 1.516 (3) | C22—H22A | 0.9300 |
C1—Fe1—C3 | 99.59 (16) | S2—C8—H8A | 107.8 |
C1—Fe1—C2 | 98.65 (15) | N1—C8—H8B | 107.8 |
C3—Fe1—C2 | 91.86 (14) | S2—C8—H8B | 107.8 |
C1—Fe1—S2 | 101.50 (11) | H8A—C8—H8B | 107.1 |
C3—Fe1—S2 | 87.84 (11) | N1—C9—C10 | 111.3 (2) |
C2—Fe1—S2 | 159.62 (10) | N1—C9—H9A | 109.4 |
C1—Fe1—S1 | 100.98 (11) | C10—C9—H9A | 109.4 |
C3—Fe1—S1 | 158.98 (12) | N1—C9—H9B | 109.4 |
C2—Fe1—S1 | 89.28 (10) | C10—C9—H9B | 109.4 |
S2—Fe1—S1 | 83.90 (3) | H9A—C9—H9B | 108.0 |
C1—Fe1—Fe2 | 146.91 (10) | C23—C10—C11 | 120.3 (2) |
C3—Fe1—Fe2 | 103.36 (12) | C23—C10—C9 | 119.1 (2) |
C2—Fe1—Fe2 | 104.04 (11) | C11—C10—C9 | 120.6 (2) |
S2—Fe1—Fe2 | 56.42 (3) | C10—C11—C12 | 124.1 (3) |
S1—Fe1—Fe2 | 56.15 (3) | C10—C11—C16 | 118.8 (2) |
C5—Fe2—C4 | 89.64 (17) | C12—C11—C16 | 117.1 (3) |
C5—Fe2—C6 | 98.69 (18) | C13—C12—C11 | 121.5 (3) |
C4—Fe2—C6 | 96.92 (15) | C13—C12—H12A | 119.2 |
C5—Fe2—S1 | 155.70 (13) | C11—C12—H12A | 119.2 |
C4—Fe2—S1 | 89.06 (12) | C12—C13—C14 | 120.8 (3) |
C6—Fe2—S1 | 105.56 (12) | C12—C13—H13A | 119.6 |
C5—Fe2—S2 | 86.13 (12) | C14—C13—H13A | 119.6 |
C4—Fe2—S2 | 153.17 (11) | C15—C14—C13 | 120.2 (3) |
C6—Fe2—S2 | 109.91 (10) | C15—C14—H14A | 119.9 |
S1—Fe2—S2 | 84.16 (3) | C13—C14—H14A | 119.9 |
C5—Fe2—Fe1 | 99.71 (13) | C14—C15—C16 | 121.3 (3) |
C4—Fe2—Fe1 | 98.44 (11) | C14—C15—H15A | 119.3 |
C6—Fe2—Fe1 | 156.02 (10) | C16—C15—H15A | 119.3 |
S1—Fe2—Fe1 | 56.56 (3) | C17—C16—C15 | 121.2 (3) |
S2—Fe2—Fe1 | 56.44 (3) | C17—C16—C11 | 119.8 (2) |
C7—S1—Fe2 | 114.67 (9) | C15—C16—C11 | 118.9 (3) |
C7—S1—Fe1 | 108.99 (10) | C18—C17—C16 | 122.0 (3) |
Fe2—S1—Fe1 | 67.30 (3) | C18—C17—H17A | 119.0 |
C8—S2—Fe2 | 116.24 (9) | C16—C17—H17A | 119.0 |
C8—S2—Fe1 | 107.69 (9) | C17—C18—C19 | 121.4 (3) |
Fe2—S2—Fe1 | 67.14 (3) | C17—C18—C23 | 119.1 (2) |
C8—N1—C7 | 115.1 (2) | C19—C18—C23 | 119.4 (3) |
C8—N1—C9 | 116.4 (2) | C20—C19—C18 | 121.1 (3) |
C7—N1—C9 | 118.4 (2) | C20—C19—H19A | 119.4 |
O1—C1—Fe1 | 178.4 (3) | C18—C19—H19A | 119.4 |
O2—C2—Fe1 | 179.5 (4) | C19—C20—C21 | 120.2 (3) |
O3—C3—Fe1 | 179.8 (4) | C19—C20—H20A | 119.9 |
O4—C4—Fe2 | 177.7 (4) | C21—C20—H20A | 119.9 |
O5—C5—Fe2 | 178.5 (4) | C22—C21—C20 | 120.8 (3) |
O6—C6—Fe2 | 177.1 (3) | C22—C21—H21A | 119.6 |
N1—C7—S1 | 120.22 (19) | C20—C21—H21A | 119.6 |
N1—C7—H7A | 107.3 | C21—C22—C23 | 121.7 (3) |
S1—C7—H7A | 107.3 | C21—C22—H22A | 119.2 |
N1—C7—H7B | 107.3 | C23—C22—H22A | 119.2 |
S1—C7—H7B | 107.3 | C10—C23—C22 | 123.4 (2) |
H7A—C7—H7B | 106.9 | C10—C23—C18 | 119.9 (2) |
N1—C8—S2 | 118.21 (18) | C22—C23—C18 | 116.8 (2) |
N1—C8—H8A | 107.8 |
Experimental details
Crystal data | |
Chemical formula | [Fe2(C17H15NS2)(CO)6] |
Mr | 577.18 |
Crystal system, space group | Orthorhombic, Pbcn |
Temperature (K) | 273 |
a, b, c (Å) | 15.234 (6), 11.945 (4), 25.840 (9) |
V (Å3) | 4702 (3) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 1.45 |
Crystal size (mm) | 0.40 × 0.22 × 0.19 |
Data collection | |
Diffractometer | Bruker SMART APEXII CCD area-detector |
Absorption correction | Multi-scan (SAINT-Plus; Bruker, 2001) |
Tmin, Tmax | 0.598, 0.775 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 26672, 5291, 3449 |
Rint | 0.053 |
(sin θ/λ)max (Å−1) | 0.646 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.085, 1.01 |
No. of reflections | 5291 |
No. of parameters | 307 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.28 |
Computer programs: SMART (Bruker, 2001), SAINT-Plus (Bruker, 2001), SAINT-Plus, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2001), SHELXTL.
Fe1—C1 | 1.786 (4) | Fe2—C5 | 1.783 (4) |
Fe1—C3 | 1.791 (3) | Fe2—C4 | 1.785 (3) |
Fe1—C2 | 1.792 (3) | Fe2—C6 | 1.797 (4) |
Fe1—S2 | 2.2643 (11) | Fe2—S1 | 2.2542 (10) |
Fe1—S1 | 2.2649 (11) | Fe2—S2 | 2.2639 (10) |
Fe1—Fe2 | 2.5040 (8) | ||
C1—Fe1—Fe2 | 146.91 (10) | C6—Fe2—Fe1 | 156.02 (10) |
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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.