Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100006399/sx1099sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100006399/sx1099Isup2.hkl |
CCDC reference: 147637
Compound (I) was synthesized following reported procedures for this type of compound (Howard et al., 1989; Pearson et al., 1992). The starting 1-chloro-cyclohexa-1,3-diene-5,6-diol, obtained by microbial oxidation of chlorobenzene (Gibson et al., 1970; Brovetto et al., 1999), was treated with methyliodide to give the dimethylether, and further reacted with Fe2(CO)9. Suitable crystals were grown as colourless plates from dichloromethane by slow cooling.
All H atoms were found in difference Fourier maps and freely refined, except those belonging to C10 which were placed at geometrically suitable positions and refined with fixed isotropic displacement parameters, Uiso = 1.2Ueq of the parent atom.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: MSC/AFC Diffractometer Control Software; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ZORTEP (Zsolnai & Pritzkow, 1995); software used to prepare material for publication: PLATON98 (Spek, 1998).
Fig. 1. The molecular view of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are drawn as spheres of arbitrary radii. |
[Fe(CO3)(C8H11O2Cl)] | Dx = 1.604 Mg m−3 |
Mr = 314.50 | Mo Kα radiation, λ = 0.71070 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 7.139 (2) Å | θ = 25.1–26.8° |
b = 26.763 (2) Å | µ = 1.37 mm−1 |
c = 6.815 (2) Å | T = 293 K |
V = 1302.0 (6) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.28 × 0.10 mm |
F(000) = 640 |
Rigaku AFC-7S diffractometer | 1793 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.056 |
Graphite monochromator | θmax = 27.5°, θmin = 3.0° |
θ/2θ scans | h = −9→9 |
Absorption correction: ψ-scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1993) | k = −32→34 |
Tmin = 0.684, Tmax = 0.875 | l = −7→8 |
1996 measured reflections | 3 standard reflections every 150 reflections |
1715 (241) independent reflections | intensity decay: 1% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.044 | Calculated w = 1/[σ2(Fo2) + (0.0877P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.119 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 1.25 e Å−3 |
1956 reflections | Δρmin = −0.76 e Å−3 |
197 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.046 (5) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.00 (3) |
[Fe(CO3)(C8H11O2Cl)] | V = 1302.0 (6) Å3 |
Mr = 314.50 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 7.139 (2) Å | µ = 1.37 mm−1 |
b = 26.763 (2) Å | T = 293 K |
c = 6.815 (2) Å | 0.30 × 0.28 × 0.10 mm |
Rigaku AFC-7S diffractometer | 1793 reflections with I > 2σ(I) |
Absorption correction: ψ-scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1993) | Rint = 0.056 |
Tmin = 0.684, Tmax = 0.875 | 3 standard reflections every 150 reflections |
1996 measured reflections | intensity decay: 1% |
1715 (241) independent reflections |
R[F2 > 2σ(F2)] = 0.044 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.119 | Δρmax = 1.25 e Å−3 |
S = 1.06 | Δρmin = −0.76 e Å−3 |
1956 reflections | Absolute structure: Flack (1983) |
197 parameters | Absolute structure parameter: 0.00 (3) |
0 restraints |
Geometry. NOT INTENDED FOR PUBLICATION 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. Least-squares planes mentioned above ——————————————————————– Plane 1 − 3.022 (11)*x + 14.35 (56)*y + 4.9778 (12)*z=2.411 (92) Atoms belonging to the previous plane and deviations (Ang.) from it: C1 0.0352 (13) C6 − 0.0583 (21) C5 0.0583 (21) C4 − 0.0351 (13) Plane 2: −3.304 (11)*x + 23.558 (26)*y + 0.714 (25)*z=3.4684 (34) Atoms belonging to the previous plane and deviations (Ang.) from it: C1 − 0.0072 (14) C2 0.0134 (25) C3 − 0.0136 (26) C4 0.0075 (14) Plane 3: −3.414 (16)*x + 21.742 (39)*y + 2.274 (14)*z=0.8893 (42) Atoms belonging to the previous plane: C9 C10 C11 Acute angles between planes (Deg.) ————————————— Plane 1, Plane 2 = 41.9 (3) Plane 2, Plane 3 = 13.8 (3) |
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 | ||
Fe | 0.01687 (7) | 0.078828 (17) | 0.05939 (7) | 0.0433 (2) | |
C10 | −0.0840 (8) | 0.01829 (16) | 0.0902 (8) | 0.0683 (12) | |
O4 | −0.1500 (8) | −0.02029 (14) | 0.1128 (8) | 0.1106 (18) | |
C9 | 0.2339 (7) | 0.05996 (15) | 0.1688 (7) | 0.0623 (10) | |
O3 | 0.3758 (6) | 0.04809 (15) | 0.2339 (8) | 0.0938 (14) | |
C11 | 0.0780 (7) | 0.07363 (14) | −0.1958 (6) | 0.0560 (9) | |
O5 | 0.1183 (8) | 0.06854 (13) | −0.3538 (5) | 0.0866 (13) | |
C1 | 0.0722 (5) | 0.15431 (12) | 0.0906 (5) | 0.0439 (7) | |
Cl | 0.29768 (15) | 0.17750 (4) | 0.14568 (18) | 0.0625 (3) | |
C2 | −0.0309 (6) | 0.13568 (14) | 0.2571 (5) | 0.0497 (8) | |
H2 | 0.020 (6) | 0.1348 (16) | 0.379 (6) | 0.048 (10)* | |
C3 | −0.1999 (6) | 0.11237 (16) | 0.2059 (6) | 0.0536 (9) | |
H3 | −0.277 (12) | 0.098 (3) | 0.279 (12) | 0.13 (3)* | |
C4 | −0.2429 (6) | 0.11338 (16) | 0.0031 (6) | 0.0520 (8) | |
H4 | −0.349 (9) | 0.0937 (19) | −0.048 (8) | 0.074 (16)* | |
C5 | −0.2193 (5) | 0.16239 (15) | −0.1050 (6) | 0.0476 (7) | |
H5 | −0.308 (7) | 0.1847 (18) | −0.052 (8) | 0.057 (13)* | |
O1 | −0.2486 (4) | 0.15781 (12) | −0.3074 (4) | 0.0573 (7) | |
C6 | −0.0198 (5) | 0.18388 (12) | −0.0693 (5) | 0.0418 (6) | |
H6 | −0.019 (8) | 0.2187 (16) | −0.020 (6) | 0.048 (11)* | |
C7 | −0.4421 (6) | 0.1571 (2) | −0.3566 (8) | 0.0757 (14) | |
H7A | −0.4552 (8) | 0.1541 (3) | −0.491 (5) | 0.091* | |
H7B | −0.497 (2) | 0.1865 (10) | −0.3155 (16) | 0.091* | |
H7C | −0.499 (2) | 0.1304 (9) | −0.296 (2) | 0.091* | |
O2 | 0.0959 (4) | 0.18149 (9) | −0.2369 (4) | 0.0468 (6) | |
C8 | 0.0940 (7) | 0.22545 (15) | −0.3529 (7) | 0.0593 (10) | |
H8A | −0.028 (7) | 0.2341 (18) | −0.404 (7) | 0.053 (12)* | |
H8B | 0.162 (7) | 0.2533 (16) | −0.278 (7) | 0.058 (13)* | |
H8C | 0.172 (8) | 0.2159 (18) | −0.475 (7) | 0.058 (14)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.0494 (3) | 0.0371 (3) | 0.0434 (3) | −0.00265 (19) | 0.0026 (2) | 0.00332 (16) |
C10 | 0.083 (3) | 0.0496 (19) | 0.072 (3) | −0.0122 (19) | 0.011 (3) | 0.002 (2) |
O4 | 0.137 (4) | 0.0566 (18) | 0.138 (4) | −0.032 (2) | 0.028 (4) | 0.009 (2) |
C9 | 0.067 (2) | 0.0514 (19) | 0.069 (2) | 0.0047 (19) | −0.006 (2) | 0.0120 (19) |
O3 | 0.073 (2) | 0.080 (2) | 0.128 (4) | 0.012 (2) | −0.023 (3) | 0.024 (2) |
C11 | 0.083 (3) | 0.0402 (16) | 0.0448 (18) | −0.0017 (17) | 0.0094 (17) | 0.0016 (14) |
O5 | 0.141 (4) | 0.0629 (17) | 0.0559 (18) | 0.018 (2) | 0.021 (2) | 0.0002 (15) |
C1 | 0.0432 (15) | 0.0397 (14) | 0.0488 (17) | −0.0027 (12) | 0.0015 (13) | −0.0024 (13) |
Cl | 0.0539 (5) | 0.0675 (6) | 0.0660 (6) | −0.0187 (4) | −0.0107 (4) | 0.0024 (5) |
C2 | 0.0575 (19) | 0.0498 (16) | 0.0417 (15) | 0.0016 (16) | 0.0042 (15) | −0.0018 (14) |
C3 | 0.0503 (19) | 0.059 (2) | 0.0512 (19) | −0.0044 (16) | 0.0170 (16) | 0.0026 (16) |
C4 | 0.0413 (17) | 0.0550 (19) | 0.060 (2) | −0.0096 (15) | 0.0056 (15) | 0.0027 (16) |
C5 | 0.0338 (13) | 0.0553 (17) | 0.0536 (19) | 0.0086 (14) | 0.0073 (13) | 0.0011 (15) |
O1 | 0.0428 (13) | 0.0762 (18) | 0.0531 (14) | 0.0079 (13) | −0.0003 (12) | 0.0028 (13) |
C6 | 0.0435 (15) | 0.0364 (13) | 0.0456 (14) | 0.0035 (12) | 0.0047 (15) | −0.0001 (11) |
C7 | 0.052 (2) | 0.106 (4) | 0.069 (3) | 0.007 (2) | −0.013 (2) | 0.007 (3) |
O2 | 0.0481 (12) | 0.0397 (10) | 0.0526 (13) | 0.0072 (10) | 0.0092 (11) | 0.0084 (10) |
C8 | 0.070 (2) | 0.0473 (17) | 0.061 (2) | 0.0049 (18) | 0.009 (2) | 0.0113 (18) |
Fe—C10 | 1.785 (4) | C3—H3 | 0.83 (8) |
Fe—C9 | 1.792 (5) | C4—C5 | 1.514 (5) |
Fe—C11 | 1.798 (4) | C4—H4 | 0.99 (6) |
Fe—C3 | 2.049 (4) | C5—O1 | 1.400 (5) |
Fe—C2 | 2.061 (4) | C5—C6 | 1.555 (5) |
Fe—C1 | 2.069 (3) | C5—H5 | 0.95 (5) |
Fe—C4 | 2.108 (4) | O1—C7 | 1.421 (5) |
C10—O4 | 1.145 (6) | C6—O2 | 1.411 (4) |
C9—O3 | 1.151 (7) | C6—H6 | 0.99 (4) |
C11—O5 | 1.123 (6) | C7—H7A | 0.9221 |
C1—C2 | 1.442 (5) | C7—H7B | 0.9221 |
C1—C6 | 1.498 (5) | C7—H7C | 0.9221 |
C1—Cl | 1.765 (4) | O2—C8 | 1.418 (4) |
C2—C3 | 1.402 (6) | C8—H8A | 0.97 (5) |
C2—H2 | 0.91 (4) | C8—H8B | 1.02 (5) |
C3—C4 | 1.416 (6) | C8—H8C | 1.03 (5) |
C10—Fe—C9 | 92.5 (2) | C2—C3—Fe | 70.5 (2) |
C10—Fe—C11 | 98.1 (2) | C4—C3—Fe | 72.3 (2) |
C9—Fe—C11 | 99.8 (2) | C2—C3—H3 | 128 (6) |
C10—Fe—C3 | 92.1 (2) | C4—C3—H3 | 117 (6) |
C9—Fe—C3 | 125.0 (2) | Fe—C3—H3 | 126 (5) |
C11—Fe—C3 | 133.5 (2) | C3—C4—C5 | 117.9 (4) |
C10—Fe—C2 | 121.8 (2) | C3—C4—Fe | 67.9 (2) |
C9—Fe—C2 | 94.5 (2) | C5—C4—Fe | 111.7 (2) |
C11—Fe—C2 | 136.85 (16) | C3—C4—H4 | 120 (3) |
C3—Fe—C2 | 39.91 (17) | C5—C4—H4 | 112 (3) |
C10—Fe—C1 | 162.0 (2) | Fe—C4—H4 | 121 (3) |
C9—Fe—C1 | 93.86 (17) | O1—C5—C4 | 112.8 (3) |
C11—Fe—C1 | 97.38 (16) | O1—C5—C6 | 108.9 (3) |
C3—Fe—C1 | 70.52 (15) | C4—C5—C6 | 110.3 (3) |
C2—Fe—C1 | 40.86 (14) | O1—C5—H5 | 110 (3) |
C10—Fe—C4 | 93.7 (2) | C4—C5—H5 | 107 (3) |
C9—Fe—C4 | 163.77 (19) | C6—C5—H5 | 109 (3) |
C11—Fe—C4 | 94.09 (19) | C5—O1—C7 | 112.3 (3) |
C3—Fe—C4 | 39.81 (17) | O2—C6—C1 | 107.9 (3) |
C2—Fe—C4 | 69.48 (17) | O2—C6—C5 | 113.1 (3) |
C1—Fe—C4 | 76.02 (15) | C1—C6—C5 | 108.7 (3) |
O4—C10—Fe | 178.8 (5) | O2—C6—H6 | 108 (3) |
O3—C9—Fe | 178.0 (5) | C1—C6—H6 | 104 (3) |
O5—C11—Fe | 177.3 (4) | C5—C6—H6 | 114 (3) |
C2—C1—C6 | 122.1 (3) | O1—C7—H7A | 109.5 |
C2—C1—Cl | 114.8 (3) | O1—C7—H7B | 109.5 |
C6—C1—Cl | 111.6 (2) | H7A—C7—H7B | 109.5 |
C2—C1—Fe | 69.24 (19) | O1—C7—H7C | 109.5 |
C6—C1—Fe | 110.9 (2) | H7A—C7—H7C | 109.5 |
Cl—C1—Fe | 122.62 (18) | H7B—C7—H7C | 109.5 |
C3—C2—C1 | 113.4 (3) | C6—O2—C8 | 114.1 (3) |
C3—C2—Fe | 69.6 (2) | O2—C8—H8A | 114 (3) |
C1—C2—Fe | 69.90 (19) | O2—C8—H8B | 109 (3) |
C3—C2—H2 | 124 (3) | H8A—C8—H8B | 116 (4) |
C1—C2—H2 | 122 (3) | O2—C8—H8C | 104 (3) |
Fe—C2—H2 | 121 (3) | H8A—C8—H8C | 105 (4) |
C2—C3—C4 | 114.9 (3) | H8B—C8—H8C | 109 (4) |
C9—Fe—C10—O4 | 95 (30) | C3—Fe—C2—C1 | −126.0 (3) |
C11—Fe—C10—O4 | −165 (30) | C4—Fe—C2—C1 | −92.2 (2) |
C3—Fe—C10—O4 | −30 (30) | C1—C2—C3—C4 | −2.8 (5) |
C2—Fe—C10—O4 | −2 (30) | Fe—C2—C3—C4 | −58.7 (3) |
C1—Fe—C10—O4 | −15 (31) | C1—C2—C3—Fe | 55.9 (3) |
C4—Fe—C10—O4 | −70 (30) | C10—Fe—C3—C2 | 141.1 (3) |
C10—Fe—C9—O3 | 116 (13) | C9—Fe—C3—C2 | 46.6 (3) |
C11—Fe—C9—O3 | 17 (13) | C11—Fe—C3—C2 | −115.7 (3) |
C3—Fe—C9—O3 | −150 (13) | C1—Fe—C3—C2 | −34.2 (2) |
C2—Fe—C9—O3 | −122 (13) | C4—Fe—C3—C2 | −125.5 (4) |
C1—Fe—C9—O3 | −81 (13) | C10—Fe—C3—C4 | −93.3 (3) |
C4—Fe—C9—O3 | −132 (13) | C9—Fe—C3—C4 | 172.1 (3) |
C10—Fe—C11—O5 | −41 (12) | C11—Fe—C3—C4 | 9.9 (4) |
C9—Fe—C11—O5 | 53 (12) | C2—Fe—C3—C4 | 125.5 (4) |
C3—Fe—C11—O5 | −141 (11) | C1—Fe—C3—C4 | 91.4 (3) |
C2—Fe—C11—O5 | 161 (11) | C2—C3—C4—C5 | −46.0 (5) |
C1—Fe—C11—O5 | 149 (12) | Fe—C3—C4—C5 | −103.7 (3) |
C4—Fe—C11—O5 | −135 (12) | C2—C3—C4—Fe | 57.7 (3) |
C10—Fe—C1—C2 | 18.0 (8) | C10—Fe—C4—C3 | 88.7 (3) |
C9—Fe—C1—C2 | −92.5 (3) | C9—Fe—C4—C3 | −23.6 (7) |
C11—Fe—C1—C2 | 167.1 (3) | C11—Fe—C4—C3 | −172.8 (3) |
C3—Fe—C1—C2 | 33.4 (2) | C2—Fe—C4—C3 | −33.9 (2) |
C4—Fe—C1—C2 | 74.7 (2) | C1—Fe—C4—C3 | −76.2 (3) |
C10—Fe—C1—C6 | −99.6 (7) | C10—Fe—C4—C5 | −158.9 (3) |
C9—Fe—C1—C6 | 149.9 (3) | C9—Fe—C4—C5 | 88.8 (7) |
C11—Fe—C1—C6 | 49.5 (3) | C11—Fe—C4—C5 | −60.4 (3) |
C3—Fe—C1—C6 | −84.2 (3) | C3—Fe—C4—C5 | 112.4 (4) |
C2—Fe—C1—C6 | −117.6 (3) | C2—Fe—C4—C5 | 78.5 (3) |
C4—Fe—C1—C6 | −42.9 (2) | C1—Fe—C4—C5 | 36.2 (3) |
C10—Fe—C1—Cl | 124.8 (6) | C3—C4—C5—O1 | 174.3 (3) |
C9—Fe—C1—Cl | 14.4 (3) | Fe—C4—C5—O1 | 98.7 (3) |
C11—Fe—C1—Cl | −86.1 (3) | C3—C4—C5—C6 | 52.4 (4) |
C3—Fe—C1—Cl | 140.3 (3) | Fe—C4—C5—C6 | −23.3 (4) |
C2—Fe—C1—Cl | 106.9 (3) | C4—C5—O1—C7 | 79.8 (5) |
C4—Fe—C1—Cl | −178.5 (3) | C6—C5—O1—C7 | −157.5 (4) |
C6—C1—C2—C3 | 46.6 (5) | C2—C1—C6—O2 | −159.9 (3) |
Cl—C1—C2—C3 | −173.1 (3) | Cl—C1—C6—O2 | 58.7 (3) |
Fe—C1—C2—C3 | −55.7 (3) | Fe—C1—C6—O2 | −81.9 (3) |
C6—C1—C2—Fe | 102.3 (3) | C2—C1—C6—C5 | −36.9 (4) |
Cl—C1—C2—Fe | −117.4 (2) | Cl—C1—C6—C5 | −178.3 (2) |
C10—Fe—C2—C3 | −47.6 (3) | Fe—C1—C6—C5 | 41.1 (3) |
C9—Fe—C2—C3 | −143.3 (3) | O1—C5—C6—O2 | −15.0 (4) |
C11—Fe—C2—C3 | 107.1 (3) | C4—C5—C6—O2 | 109.2 (3) |
C1—Fe—C2—C3 | 126.0 (3) | O1—C5—C6—C1 | −134.8 (3) |
C4—Fe—C2—C3 | 33.8 (2) | C4—C5—C6—C1 | −10.6 (4) |
C10—Fe—C2—C1 | −173.6 (3) | C1—C6—O2—C8 | −146.3 (3) |
C9—Fe—C2—C1 | 90.7 (3) | C5—C6—O2—C8 | 93.4 (4) |
C11—Fe—C2—C1 | −18.9 (4) |
Experimental details
Crystal data | |
Chemical formula | [Fe(CO3)(C8H11O2Cl)] |
Mr | 314.50 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 7.139 (2), 26.763 (2), 6.815 (2) |
V (Å3) | 1302.0 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.37 |
Crystal size (mm) | 0.30 × 0.28 × 0.10 |
Data collection | |
Diffractometer | Rigaku AFC-7S diffractometer |
Absorption correction | ψ-scan (MSC/AFC Diffractometer Control Software; Molecular Structure Corporation, 1993) |
Tmin, Tmax | 0.684, 0.875 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1996, 1715 (241), 1793 |
Rint | 0.056 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.119, 1.06 |
No. of reflections | 1956 |
No. of parameters | 197 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 1.25, −0.76 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.00 (3) |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), ZORTEP (Zsolnai & Pritzkow, 1995), PLATON98 (Spek, 1998).
Fe—C10 | 1.785 (4) | C1—C2 | 1.442 (5) |
Fe—C9 | 1.792 (5) | C1—C6 | 1.498 (5) |
Fe—C11 | 1.798 (4) | C2—C3 | 1.402 (6) |
Fe—C3 | 2.049 (4) | C3—C4 | 1.416 (6) |
Fe—C2 | 2.061 (4) | C4—C5 | 1.514 (5) |
Fe—C1 | 2.069 (3) | C5—C6 | 1.555 (5) |
Fe—C4 | 2.108 (4) | ||
C3—Fe—C2 | 39.91 (17) | C3—C2—C1 | 113.4 (3) |
C3—Fe—C1 | 70.52 (15) | C2—C3—C4 | 114.9 (3) |
C2—Fe—C1 | 40.86 (14) | C3—C4—C5 | 117.9 (4) |
C3—Fe—C4 | 39.81 (17) | C4—C5—C6 | 110.3 (3) |
C1—Fe—C4 | 76.02 (15) | C1—C6—C5 | 108.7 (3) |
C2—C1—C6 | 122.1 (3) | ||
C6—C1—C2—C3 | 46.6 (5) | C3—C4—C5—C6 | 52.4 (4) |
C1—C2—C3—C4 | −2.8 (5) | C2—C1—C6—C5 | −36.9 (4) |
C2—C3—C4—C5 | −46.0 (5) | C4—C5—C6—C1 | −10.6 (4) |
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The title compound, (I), is a transition metal tricarbonyl and diene π-complex. These kinds of compounds are used extensively in organic synthesis. Those in which the diene has chiral centres are particularly useful because they offer an efficient approach to enantioselective synthesis. It has been reported that the stereocontrol is produced by the metal centre, which effectively hinders access to one side of the molecule (Johnson et al., 1977; Howard et al., 1989). The chiral dienic system in the present structure was prepared by microbial dioxygenation of chlorobenzene (Gibson et al., 1970; Brovetto et al., 1999) to give a homochiral cis-diol, followed by further treatment with methyliodide to obtain the cis-dimethylether. \sch
Fig. 1 shows the molecular structure of (I). The metal-ligand arrangement is similar to that observed in other (cyclohexa-1,3-diene)tricarbonyliron derivatives (Dunand & Robertson, 1982). All bond distances and angles (Table 1) are within the range of expected values (Guy et al., 1976; Anderson & Robertson, 1984).
The determination of the absolute configuration of the molecule agrees with that of the parent dienic cis-diol (Gibson et al., 1970). The chiral centres C5 and C6 (arising from the original enzymatic synthesis) are R and S, respectively. The descriptor for the entire complex is S because the fiduciary atom C1 (bonded to Fe and Cl) is in the S configuration. For all assignments of configuration, the occurrence of bonding to Fe was taken into account.
The diene moiety, C1/C2/C3/C4, is planar. The maximum absolute deviation from the mean plane is 0.014 (3) Å for C3. On the other hand, the planarity of the set C1/C6/C5/C4 is lower, with a maximum absolute deviation 0.06 (2) Å for C5 and C6. The dihedral angle of 41.9 (3)° between the two planes agrees well with the values observed for tricarbonyl[2–5-η-(dimethyl 2,4-cyclohexadiene-1α,2-dicarboxylate)]iron(0) (42.1°; Dunand & Robertson, 1982*), tricarbonyl[2–5-η-(methyl 1α-phenyl-2,4-cyclohexadiene-1β-carboxylate)]iron(0) (42.2**°; Anderson et al., 1982) and tricarbonyl{(4–7-η)-3-acetyl-3a,7a-dihydro-6-methoxy-2-methylbenzo[b]furan)} iron(0) (41.7°; Anderson & Robertson, 1983). Such a high value is characteristic of systems containing both electron-donating and electron-withdrawing ring substituents, as previously reported by Anderson & Robertson (1983). *please check - name and angle are for paper at B38, 2037–2040. **given as 42.4° in orig CIF, 42.2° where cited in B38 2034–2037.
The Fe(CO)3 group and all the substituents are located on the same side of the six-membered ring. The carbonyl (C9/C10/C11) and the diene (C1/C2/C3/C4) planes are not parallel; the dihedral angle between these planes is 13.8 (3)°, with the carbonyl ligand –C10═O4 closer to the diene plane. Atom O2 of the methoxy group bonded to C6 is in relatively close contact with the carbonyl group –C11═O5, with separations O2···C11 2.903 (5) and O2···O5 3.130 (4) Å.
The presence of the Cl atom (an electron-withdrawing substituent) bonded to C1 removes the C1—C2, C3—C4 bond-length similarity (Dunand & Robertson, 1982), with the C1—C2 bond distance of 1.442 (5) Å significantly longer than the C3—C4 bond distance of 1.416 (6) Å.
The absence of hydrogen bonds and π-contacts suggest that the crystal packing is directed by van der Waals forces.
Our results are consistent with the mechanism described in a previous report (Howard et al., 1989), where the methoxy groups were considered to play an important role in the diastereoface selectivity of the complexation. According to that work, the complexation should first occur via the O atoms belonging to the methoxy groups and take place finally through the more favourable dienic system. Thus, the present work, which demonstrates that the binding of the iron tricarbonyl moiety is located on the same side of the six-membered ring as the methoxy substituents, supports the importance of the methoxy groups for stereocontrol in these homochiral-complexes with planar chirality, making them useful reagents in chiral synthesis.