Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103011703/gd1251sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103011703/gd1251Isup2.hkl |
CCDC reference: 219553
NaBH4 (253 mg, 6.7 mmol) was added gradually to a solution of methyl 2-(ferrocenoyl)benzenacetate (326 mg, 0.9 mmol) in a mixture of EtOH/Et2O (1:1 v/v; 5 cm3). The mixture was refluxed for 2 h and worked up in the usual manner. Separation by preparative thin-layer chromatography on silica gel (Merck, Kieselgel 60 HF254) gave 2-(α-hydroxyferrocyl)benzenethanol (237 mg; yield 78%) and 1-ferrocenylisochromane (57 mg; yield 20%; yellow crystals; m.p. 365–366 K). Single crystals of the title compound were obtained by slow evaporation from cyclohexane solution at room temperature. IR (CH2Cl2, υ, cm−1): 3081 (w) and 3020 (w) (C—H, Fc), 2942 (m) (C—H, aliphatic), 1278 (m) (C—O—C); 1H NMR (DMSO, p.p.m.): δ 7.18 (d, 1H, H16), 7.12 (d, 1H, H17), 7.14 (d, 1H, H18), 7.16 (d, 1H, H19), 4.23 (s, 5H, unsubstituted ferrocene ring), 4.13–4.20 (m, 4H, substituted ferrocene ring), 3.97 (m, 1H, Ha15), 3.77 (m, 1H, Hb15), 2.78 (m, 2H, H14), 5.58 (s, 1H, H11). 13C NMR (DMSO, p.p.m.): δ 137.29 (C12), 132.91 (C13), 128.5 (C17), 126.25 (C18), 125.98 (C16), 125.36 (C19), 90.21 (C1), 73.63 (C11), 68.62 (unsubstituted ferrocene ring), 68.56–66.31 (substituted ferrocene ring), 61.55 (C15), 27.99 (C14).
All H atoms were included in calculated positions as riding atoms, with SHELXL97 (Sheldrick, 1997) defaults.
Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997); data reduction: DENZO–SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97.
[Fe(C5H5)(C14H13O)] | F(000) = 664 |
Mr = 318.18 | Dx = 1.442 Mg m−3 |
Monoclinic, P21/c | Melting point = 365–366 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.5053 (2) Å | Cell parameters from 3411 reflections |
b = 18.5095 (3) Å | θ = 2.6–27.5° |
c = 7.1941 (1) Å | µ = 1.02 mm−1 |
β = 106.933 (1)° | T = 293 K |
V = 1465.62 (4) Å3 | Prism, orange |
Z = 4 | 0.80 × 0.40 × 0.15 mm |
Nonius KappaCCD area-detector diffractometer | 3334 independent reflections |
Radiation source: fine-focus sealed tube | 2662 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.064 |
ϕ and ω scans | θmax = 27.4°, θmin = 3.7° |
Absorption correction: multi-scan (DENZO–SMN; Otwinovski & Minor, 1997) | h = −14→14 |
Tmin = 0.630, Tmax = 0.857 | k = −23→23 |
16885 measured reflections | l = −9→9 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.030 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0341P)2 + 0.3545P] where P = (Fo2 + 2Fc2)/3 |
3334 reflections | (Δ/σ)max = 0.001 |
190 parameters | Δρmax = 0.25 e Å−3 |
0 restraints | Δρmin = −0.23 e Å−3 |
[Fe(C5H5)(C14H13O)] | V = 1465.62 (4) Å3 |
Mr = 318.18 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 11.5053 (2) Å | µ = 1.02 mm−1 |
b = 18.5095 (3) Å | T = 293 K |
c = 7.1941 (1) Å | 0.80 × 0.40 × 0.15 mm |
β = 106.933 (1)° |
Nonius KappaCCD area-detector diffractometer | 3334 independent reflections |
Absorption correction: multi-scan (DENZO–SMN; Otwinovski & Minor, 1997) | 2662 reflections with I > 2σ(I) |
Tmin = 0.630, Tmax = 0.857 | Rint = 0.064 |
16885 measured reflections |
R[F2 > 2σ(F2)] = 0.030 | 0 restraints |
wR(F2) = 0.076 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.25 e Å−3 |
3334 reflections | Δρmin = −0.23 e Å−3 |
190 parameters |
x | y | z | Uiso*/Ueq | ||
Fe | 0.16848 (2) | 0.110779 (12) | 0.96688 (3) | 0.03127 (9) | |
O1 | 0.40898 (11) | 0.15661 (7) | 0.79838 (17) | 0.0449 (3) | |
C1 | 0.35320 (15) | 0.10725 (8) | 1.0671 (2) | 0.0322 (4) | |
C2 | 0.30923 (15) | 0.16871 (9) | 1.1433 (2) | 0.0361 (4) | |
H2 | 0.3285 | 0.2166 | 1.1263 | 0.043* | |
C3 | 0.23038 (17) | 0.14429 (11) | 1.2505 (2) | 0.0425 (4) | |
H3 | 0.1893 | 0.1735 | 1.3156 | 0.051* | |
C4 | 0.22539 (17) | 0.06823 (11) | 1.2408 (2) | 0.0439 (4) | |
H4 | 0.1803 | 0.0386 | 1.2981 | 0.053* | |
C5 | 0.30114 (15) | 0.04481 (9) | 1.1282 (2) | 0.0382 (4) | |
H5 | 0.3146 | −0.0029 | 1.0993 | 0.046* | |
C6 | 0.12264 (18) | 0.09281 (12) | 0.6764 (3) | 0.0522 (5) | |
H6 | 0.1750 | 0.0762 | 0.6088 | 0.063* | |
C7 | 0.10194 (18) | 0.16512 (13) | 0.7126 (3) | 0.0556 (6) | |
H7 | 0.1378 | 0.2050 | 0.6730 | 0.067* | |
C8 | 0.01692 (18) | 0.16689 (12) | 0.8202 (3) | 0.0542 (5) | |
H8 | −0.0130 | 0.2081 | 0.8642 | 0.065* | |
C9 | −0.01449 (17) | 0.09493 (12) | 0.8491 (3) | 0.0512 (5) | |
H9 | −0.0687 | 0.0803 | 0.9155 | 0.061* | |
C10 | 0.05068 (17) | 0.04954 (11) | 0.7596 (3) | 0.0502 (5) | |
H10 | 0.0470 | −0.0006 | 0.7560 | 0.060* | |
C11 | 0.44362 (15) | 0.10553 (9) | 0.9526 (2) | 0.0335 (4) | |
H11 | 0.4406 | 0.0574 | 0.8949 | 0.040* | |
C12 | 0.57296 (15) | 0.11842 (8) | 1.0803 (2) | 0.0330 (4) | |
C13 | 0.65379 (15) | 0.15786 (9) | 1.0078 (3) | 0.0380 (4) | |
C14 | 0.61242 (18) | 0.19005 (11) | 0.8074 (3) | 0.0503 (5) | |
H14A | 0.6017 | 0.2417 | 0.8173 | 0.060* | |
H14B | 0.6743 | 0.1823 | 0.7424 | 0.060* | |
C15 | 0.49509 (17) | 0.15690 (12) | 0.6892 (3) | 0.0500 (5) | |
H15A | 0.4628 | 0.1843 | 0.5704 | 0.060* | |
H15B | 0.5095 | 0.1078 | 0.6543 | 0.060* | |
C16 | 0.61290 (17) | 0.09005 (10) | 1.2667 (3) | 0.0429 (4) | |
H16 | 0.5592 | 0.0638 | 1.3152 | 0.051* | |
C17 | 0.7312 (2) | 0.10010 (11) | 1.3818 (3) | 0.0563 (5) | |
H17 | 0.7567 | 0.0806 | 1.5062 | 0.068* | |
C18 | 0.81117 (19) | 0.13925 (13) | 1.3109 (3) | 0.0612 (6) | |
H18 | 0.8907 | 0.1464 | 1.3874 | 0.073* | |
C19 | 0.77228 (17) | 0.16769 (11) | 1.1260 (3) | 0.0519 (5) | |
H19 | 0.8265 | 0.1941 | 1.0790 | 0.062* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Fe | 0.02969 (14) | 0.03641 (15) | 0.02777 (13) | −0.00313 (10) | 0.00846 (10) | −0.00124 (10) |
O1 | 0.0360 (7) | 0.0639 (8) | 0.0356 (6) | 0.0098 (6) | 0.0118 (5) | 0.0147 (6) |
C1 | 0.0283 (8) | 0.0367 (9) | 0.0289 (8) | −0.0014 (7) | 0.0041 (6) | −0.0005 (7) |
C2 | 0.0360 (9) | 0.0370 (9) | 0.0335 (8) | −0.0052 (7) | 0.0074 (7) | −0.0061 (7) |
C3 | 0.0427 (10) | 0.0570 (12) | 0.0292 (8) | −0.0017 (9) | 0.0125 (8) | −0.0073 (8) |
C4 | 0.0455 (11) | 0.0539 (11) | 0.0326 (9) | −0.0078 (9) | 0.0118 (8) | 0.0093 (8) |
C5 | 0.0406 (10) | 0.0341 (9) | 0.0379 (9) | 0.0012 (7) | 0.0082 (8) | 0.0043 (7) |
C6 | 0.0442 (11) | 0.0818 (15) | 0.0281 (9) | −0.0041 (10) | 0.0068 (8) | −0.0091 (9) |
C7 | 0.0494 (12) | 0.0699 (14) | 0.0370 (10) | −0.0165 (10) | −0.0040 (9) | 0.0175 (10) |
C8 | 0.0457 (11) | 0.0554 (12) | 0.0506 (11) | 0.0134 (10) | −0.0033 (9) | −0.0039 (10) |
C9 | 0.0299 (10) | 0.0766 (15) | 0.0458 (11) | −0.0094 (9) | 0.0089 (8) | 0.0015 (10) |
C10 | 0.0464 (11) | 0.0513 (11) | 0.0453 (10) | −0.0115 (9) | 0.0013 (9) | −0.0095 (9) |
C11 | 0.0318 (9) | 0.0362 (9) | 0.0315 (8) | 0.0014 (7) | 0.0076 (7) | 0.0000 (7) |
C12 | 0.0316 (9) | 0.0325 (9) | 0.0337 (8) | 0.0052 (7) | 0.0078 (7) | −0.0033 (7) |
C13 | 0.0343 (9) | 0.0379 (9) | 0.0430 (9) | 0.0014 (7) | 0.0132 (8) | −0.0067 (7) |
C14 | 0.0500 (12) | 0.0556 (12) | 0.0509 (11) | −0.0018 (9) | 0.0238 (9) | 0.0041 (9) |
C15 | 0.0472 (11) | 0.0713 (13) | 0.0345 (9) | 0.0066 (10) | 0.0165 (8) | 0.0096 (9) |
C16 | 0.0423 (11) | 0.0441 (10) | 0.0389 (9) | 0.0062 (8) | 0.0065 (8) | 0.0007 (8) |
C17 | 0.0507 (12) | 0.0624 (13) | 0.0445 (11) | 0.0165 (10) | −0.0039 (9) | 0.0001 (9) |
C18 | 0.0338 (11) | 0.0731 (14) | 0.0648 (14) | 0.0064 (10) | −0.0042 (10) | −0.0163 (12) |
C19 | 0.0343 (10) | 0.0577 (12) | 0.0646 (13) | −0.0037 (9) | 0.0160 (9) | −0.0131 (10) |
Fe—C6 | 2.0285 (18) | C7—C8 | 1.414 (3) |
Fe—C5 | 2.0337 (17) | C7—H7 | 0.93 |
Fe—C7 | 2.0316 (18) | C8—C9 | 1.411 (3) |
Fe—C1 | 2.0368 (16) | C8—H8 | 0.93 |
Fe—C10 | 2.0414 (18) | C9—C10 | 1.401 (3) |
Fe—C8 | 2.0399 (19) | C9—H9 | 0.93 |
Fe—C4 | 2.0445 (17) | C10—H10 | 0.93 |
Fe—C2 | 2.0458 (16) | C11—C12 | 1.523 (2) |
Fe—C9 | 2.0486 (19) | C11—H11 | 0.98 |
Fe—C3 | 2.0512 (17) | C12—C16 | 1.388 (2) |
O1—C11 | 1.4236 (19) | C12—C13 | 1.397 (2) |
O1—C15 | 1.432 (2) | C13—C19 | 1.392 (3) |
C1—C2 | 1.419 (2) | C13—C14 | 1.504 (3) |
C1—C5 | 1.429 (2) | C14—C15 | 1.501 (3) |
C1—C11 | 1.503 (2) | C14—H14A | 0.97 |
C2—C3 | 1.424 (2) | C14—H14B | 0.97 |
C2—H2 | 0.93 | C15—H15A | 0.97 |
C3—C4 | 1.410 (3) | C15—H15B | 0.97 |
C3—H3 | 0.93 | C16—C17 | 1.384 (3) |
C4—C5 | 1.419 (2) | C16—H16 | 0.93 |
C4—H4 | 0.93 | C17—C18 | 1.380 (3) |
C5—H5 | 0.93 | C17—H17 | 0.93 |
C6—C7 | 1.397 (3) | C18—C19 | 1.379 (3) |
C6—C10 | 1.405 (3) | C18—H18 | 0.93 |
C6—H6 | 0.93 | C19—H19 | 0.93 |
C6—Fe—C5 | 114.59 (8) | C4—C5—Fe | 70.04 (10) |
C6—Fe—C7 | 40.26 (9) | C1—C5—Fe | 69.57 (9) |
C5—Fe—C7 | 146.55 (8) | C4—C5—H5 | 126.0 |
C6—Fe—C1 | 106.90 (7) | C1—C5—H5 | 126.0 |
C5—Fe—C1 | 41.10 (6) | Fe—C5—H5 | 126.0 |
C7—Fe—C1 | 114.53 (7) | C7—C6—C10 | 108.22 (18) |
C6—Fe—C10 | 40.39 (8) | C7—C6—Fe | 69.99 (10) |
C5—Fe—C10 | 108.16 (8) | C10—C6—Fe | 70.30 (10) |
C7—Fe—C10 | 67.76 (9) | C7—C6—H6 | 125.9 |
C1—Fe—C10 | 130.02 (7) | C10—C6—H6 | 125.9 |
C6—Fe—C8 | 67.92 (9) | Fe—C6—H6 | 125.4 |
C5—Fe—C8 | 170.87 (8) | C6—C7—C8 | 107.90 (18) |
C7—Fe—C8 | 40.63 (9) | C6—C7—Fe | 69.75 (11) |
C1—Fe—C8 | 147.79 (8) | C8—C7—Fe | 70.00 (11) |
C10—Fe—C8 | 67.62 (8) | C6—C7—H7 | 126.1 |
C6—Fe—C4 | 147.56 (9) | C8—C7—H7 | 126.1 |
C5—Fe—C4 | 40.74 (7) | Fe—C7—H7 | 125.8 |
C7—Fe—C4 | 171.61 (9) | C7—C8—C9 | 107.83 (19) |
C1—Fe—C4 | 68.80 (7) | C7—C8—Fe | 69.37 (11) |
C10—Fe—C4 | 116.62 (8) | C9—C8—Fe | 70.14 (11) |
C8—Fe—C4 | 132.86 (8) | C7—C8—H8 | 126.1 |
C6—Fe—C2 | 130.27 (8) | C9—C8—H8 | 126.1 |
C5—Fe—C2 | 68.52 (7) | Fe—C8—H8 | 126.0 |
C7—Fe—C2 | 108.76 (8) | C10—C9—C8 | 107.72 (18) |
C1—Fe—C2 | 40.66 (6) | C10—C9—Fe | 69.69 (11) |
C10—Fe—C2 | 168.88 (7) | C8—C9—Fe | 69.48 (11) |
C8—Fe—C2 | 117.19 (8) | C10—C9—H9 | 126.1 |
C4—Fe—C2 | 68.32 (7) | C8—C9—H9 | 126.1 |
C6—Fe—C9 | 67.84 (8) | Fe—C9—H9 | 126.3 |
C5—Fe—C9 | 131.31 (8) | C9—C10—C6 | 108.33 (18) |
C7—Fe—C9 | 68.04 (8) | C9—C10—Fe | 70.24 (11) |
C1—Fe—C9 | 169.25 (8) | C6—C10—Fe | 69.31 (10) |
C10—Fe—C9 | 40.06 (8) | C9—C10—H10 | 125.8 |
C8—Fe—C9 | 40.38 (8) | C6—C10—H10 | 125.8 |
C4—Fe—C9 | 110.22 (8) | Fe—C10—H10 | 126.2 |
C2—Fe—C9 | 149.77 (8) | O1—C11—C1 | 109.37 (13) |
C6—Fe—C3 | 170.09 (8) | O1—C11—C12 | 111.64 (13) |
C5—Fe—C3 | 68.19 (7) | C1—C11—C12 | 112.14 (13) |
C7—Fe—C3 | 132.56 (9) | O1—C11—H11 | 107.8 |
C1—Fe—C3 | 68.50 (7) | C1—C11—H11 | 107.8 |
C10—Fe—C3 | 149.16 (8) | C12—C11—H11 | 107.8 |
C8—Fe—C3 | 110.94 (8) | C16—C12—C13 | 119.28 (16) |
C4—Fe—C3 | 40.27 (8) | C16—C12—C11 | 120.93 (15) |
C2—Fe—C3 | 40.69 (7) | C13—C12—C11 | 119.77 (14) |
C9—Fe—C3 | 118.17 (8) | C19—C13—C12 | 118.71 (17) |
C11—O1—C15 | 110.39 (13) | C19—C13—C14 | 120.90 (17) |
C2—C1—C5 | 107.52 (15) | C12—C13—C14 | 120.38 (16) |
C2—C1—C11 | 127.61 (14) | C15—C14—C13 | 111.24 (15) |
C5—C1—C11 | 124.78 (14) | C15—C14—H14A | 109.4 |
C2—C1—Fe | 70.01 (9) | C13—C14—H14A | 109.4 |
C5—C1—Fe | 69.33 (9) | C15—C14—H14B | 109.4 |
C11—C1—Fe | 128.61 (11) | C13—C14—H14B | 109.4 |
C1—C2—C3 | 108.05 (15) | H14A—C14—H14B | 108.0 |
C1—C2—Fe | 69.33 (9) | O1—C15—C14 | 110.04 (15) |
C3—C2—Fe | 69.86 (10) | O1—C15—H15A | 109.7 |
C1—C2—H2 | 126.0 | C14—C15—H15A | 109.7 |
C3—C2—H2 | 126.0 | O1—C15—H15B | 109.7 |
Fe—C2—H2 | 126.4 | C14—C15—H15B | 109.7 |
C4—C3—C2 | 108.26 (15) | H15A—C15—H15B | 108.2 |
C4—C3—Fe | 69.61 (10) | C17—C16—C12 | 121.22 (19) |
C2—C3—Fe | 69.45 (9) | C17—C16—H16 | 119.4 |
C4—C3—H3 | 125.9 | C12—C16—H16 | 119.4 |
C2—C3—H3 | 125.9 | C18—C17—C16 | 119.65 (19) |
Fe—C3—H3 | 126.6 | C18—C17—H17 | 120.2 |
C3—C4—C5 | 108.07 (15) | C16—C17—H17 | 120.2 |
C3—C4—Fe | 70.12 (10) | C17—C18—C19 | 119.55 (19) |
C5—C4—Fe | 69.22 (9) | C17—C18—H18 | 120.2 |
C3—C4—H4 | 126.0 | C19—C18—H18 | 120.2 |
C5—C4—H4 | 126.0 | C18—C19—C13 | 121.59 (19) |
Fe—C4—H4 | 126.3 | C18—C19—H19 | 119.2 |
C4—C5—C1 | 108.10 (15) | C13—C19—H19 | 119.2 |
C6—Fe—C1—C2 | 133.08 (11) | C5—Fe—C6—C10 | 89.48 (13) |
C5—Fe—C1—C2 | −118.66 (14) | C7—Fe—C6—C10 | −118.94 (18) |
C7—Fe—C1—C2 | 90.64 (12) | C1—Fe—C6—C10 | 132.84 (12) |
C10—Fe—C1—C2 | 171.43 (11) | C8—Fe—C6—C10 | −80.96 (14) |
C8—Fe—C1—C2 | 57.85 (17) | C4—Fe—C6—C10 | 55.94 (19) |
C4—Fe—C1—C2 | −81.00 (11) | C2—Fe—C6—C10 | 171.43 (11) |
C9—Fe—C1—C2 | −167.8 (4) | C9—Fe—C6—C10 | −37.21 (12) |
C3—Fe—C1—C2 | −37.62 (10) | C10—C6—C7—C8 | 0.3 (2) |
C6—Fe—C1—C5 | −108.26 (11) | Fe—C6—C7—C8 | −59.86 (13) |
C7—Fe—C1—C5 | −150.70 (11) | C10—C6—C7—Fe | 60.16 (13) |
C10—Fe—C1—C5 | −69.91 (13) | C5—Fe—C7—C6 | 51.74 (19) |
C8—Fe—C1—C5 | 176.50 (13) | C1—Fe—C7—C6 | 87.45 (12) |
C4—Fe—C1—C5 | 37.66 (10) | C10—Fe—C7—C6 | −37.79 (12) |
C2—Fe—C1—C5 | 118.66 (14) | C8—Fe—C7—C6 | −118.87 (17) |
C9—Fe—C1—C5 | −49.2 (4) | C2—Fe—C7—C6 | 130.93 (12) |
C3—Fe—C1—C5 | 81.04 (11) | C9—Fe—C7—C6 | −81.18 (13) |
C6—Fe—C1—C11 | 10.36 (16) | C3—Fe—C7—C6 | 170.10 (11) |
C5—Fe—C1—C11 | 118.62 (18) | C6—Fe—C7—C8 | 118.87 (17) |
C7—Fe—C1—C11 | −32.08 (17) | C5—Fe—C7—C8 | 170.61 (13) |
C10—Fe—C1—C11 | 48.71 (18) | C1—Fe—C7—C8 | −153.68 (12) |
C8—Fe—C1—C11 | −64.9 (2) | C10—Fe—C7—C8 | 81.08 (13) |
C4—Fe—C1—C11 | 156.28 (16) | C2—Fe—C7—C8 | −110.20 (13) |
C2—Fe—C1—C11 | −122.72 (18) | C9—Fe—C7—C8 | 37.69 (12) |
C9—Fe—C1—C11 | 69.5 (4) | C3—Fe—C7—C8 | −71.02 (15) |
C3—Fe—C1—C11 | −160.34 (16) | C6—C7—C8—C9 | −0.1 (2) |
C5—C1—C2—C3 | −0.09 (19) | Fe—C7—C8—C9 | −59.84 (13) |
C11—C1—C2—C3 | −176.75 (16) | C6—C7—C8—Fe | 59.70 (13) |
Fe—C1—C2—C3 | 59.33 (12) | C6—Fe—C8—C7 | −37.64 (12) |
C5—C1—C2—Fe | −59.43 (11) | C1—Fe—C8—C7 | 49.2 (2) |
C11—C1—C2—Fe | 123.92 (17) | C10—Fe—C8—C7 | −81.44 (13) |
C6—Fe—C2—C1 | −66.33 (14) | C4—Fe—C8—C7 | 172.35 (12) |
C5—Fe—C2—C1 | 38.31 (10) | C2—Fe—C8—C7 | 87.51 (13) |
C7—Fe—C2—C1 | −106.11 (11) | C9—Fe—C8—C7 | −118.94 (18) |
C10—Fe—C2—C1 | −36.3 (4) | C3—Fe—C8—C7 | 131.77 (13) |
C8—Fe—C2—C1 | −149.51 (11) | C6—Fe—C8—C9 | 81.29 (13) |
C4—Fe—C2—C1 | 82.27 (11) | C7—Fe—C8—C9 | 118.94 (18) |
C9—Fe—C2—C1 | 175.52 (13) | C1—Fe—C8—C9 | 168.11 (12) |
C3—Fe—C2—C1 | 119.42 (15) | C10—Fe—C8—C9 | 37.50 (12) |
C6—Fe—C2—C3 | 174.25 (12) | C4—Fe—C8—C9 | −68.71 (15) |
C5—Fe—C2—C3 | −81.11 (11) | C2—Fe—C8—C9 | −153.55 (11) |
C7—Fe—C2—C3 | 134.47 (12) | C3—Fe—C8—C9 | −109.29 (12) |
C1—Fe—C2—C3 | −119.42 (15) | C7—C8—C9—C10 | −0.1 (2) |
C10—Fe—C2—C3 | −155.7 (4) | Fe—C8—C9—C10 | −59.43 (13) |
C8—Fe—C2—C3 | 91.07 (13) | C7—C8—C9—Fe | 59.36 (13) |
C4—Fe—C2—C3 | −37.15 (11) | C6—Fe—C9—C10 | 37.50 (12) |
C9—Fe—C2—C3 | 56.10 (19) | C5—Fe—C9—C10 | −66.40 (15) |
C1—C2—C3—C4 | −0.03 (19) | C7—Fe—C9—C10 | 81.10 (14) |
Fe—C2—C3—C4 | 58.97 (12) | C1—Fe—C9—C10 | −24.9 (4) |
C1—C2—C3—Fe | −59.00 (11) | C8—Fe—C9—C10 | 119.01 (17) |
C5—Fe—C3—C4 | −37.79 (10) | C4—Fe—C9—C10 | −107.70 (13) |
C7—Fe—C3—C4 | 173.71 (11) | C2—Fe—C9—C10 | 170.91 (13) |
C1—Fe—C3—C4 | −82.16 (11) | C3—Fe—C9—C10 | −151.22 (12) |
C10—Fe—C3—C4 | 51.3 (2) | C6—Fe—C9—C8 | −81.51 (13) |
C8—Fe—C3—C4 | 132.46 (12) | C5—Fe—C9—C8 | 174.59 (11) |
C2—Fe—C3—C4 | −119.76 (15) | C7—Fe—C9—C8 | −37.91 (13) |
C9—Fe—C3—C4 | 88.54 (13) | C1—Fe—C9—C8 | −143.9 (4) |
C5—Fe—C3—C2 | 81.97 (11) | C10—Fe—C9—C8 | −119.01 (17) |
C7—Fe—C3—C2 | −66.54 (14) | C4—Fe—C9—C8 | 133.29 (12) |
C1—Fe—C3—C2 | 37.59 (10) | C2—Fe—C9—C8 | 51.9 (2) |
C10—Fe—C3—C2 | 171.09 (14) | C3—Fe—C9—C8 | 89.77 (13) |
C8—Fe—C3—C2 | −107.79 (12) | C8—C9—C10—C6 | 0.3 (2) |
C4—Fe—C3—C2 | 119.76 (15) | Fe—C9—C10—C6 | −59.03 (13) |
C9—Fe—C3—C2 | −151.71 (11) | C8—C9—C10—Fe | 59.29 (13) |
C2—C3—C4—C5 | 0.15 (19) | C7—C6—C10—C9 | −0.4 (2) |
Fe—C3—C4—C5 | 59.02 (12) | Fe—C6—C10—C9 | 59.61 (13) |
C2—C3—C4—Fe | −58.87 (12) | C7—C6—C10—Fe | −59.96 (13) |
C6—Fe—C4—C3 | 169.69 (13) | C6—Fe—C10—C9 | −119.54 (18) |
C5—Fe—C4—C3 | 119.34 (15) | C5—Fe—C10—C9 | 133.58 (12) |
C1—Fe—C4—C3 | 81.36 (11) | C7—Fe—C10—C9 | −81.87 (14) |
C10—Fe—C4—C3 | −153.40 (11) | C1—Fe—C10—C9 | 174.11 (11) |
C8—Fe—C4—C3 | −70.05 (15) | C8—Fe—C10—C9 | −37.79 (12) |
C2—Fe—C4—C3 | 37.52 (10) | C4—Fe—C10—C9 | 90.27 (13) |
C9—Fe—C4—C3 | −110.09 (12) | C2—Fe—C10—C9 | −155.7 (4) |
C6—Fe—C4—C5 | 50.35 (18) | C3—Fe—C10—C9 | 55.9 (2) |
C1—Fe—C4—C5 | −37.98 (10) | C5—Fe—C10—C6 | −106.88 (13) |
C10—Fe—C4—C5 | 87.26 (12) | C7—Fe—C10—C6 | 37.67 (12) |
C8—Fe—C4—C5 | 170.61 (11) | C1—Fe—C10—C6 | −66.36 (15) |
C2—Fe—C4—C5 | −81.82 (11) | C8—Fe—C10—C6 | 81.75 (14) |
C9—Fe—C4—C5 | 130.57 (11) | C4—Fe—C10—C6 | −150.20 (12) |
C3—Fe—C4—C5 | −119.34 (15) | C2—Fe—C10—C6 | −36.1 (4) |
C3—C4—C5—C1 | −0.20 (19) | C9—Fe—C10—C6 | 119.54 (18) |
Fe—C4—C5—C1 | 59.37 (11) | C3—Fe—C10—C6 | 175.43 (14) |
C3—C4—C5—Fe | −59.58 (12) | C15—O1—C11—C1 | 178.95 (14) |
C2—C1—C5—C4 | 0.18 (19) | C15—O1—C11—C12 | 54.27 (18) |
C11—C1—C5—C4 | 176.96 (15) | C2—C1—C11—O1 | −49.6 (2) |
Fe—C1—C5—C4 | −59.67 (12) | C5—C1—C11—O1 | 134.26 (16) |
C2—C1—C5—Fe | 59.86 (11) | Fe—C1—C11—O1 | 43.98 (19) |
C11—C1—C5—Fe | −123.37 (16) | C2—C1—C11—C12 | 74.8 (2) |
C6—Fe—C5—C4 | −152.99 (11) | C5—C1—C11—C12 | −101.35 (18) |
C7—Fe—C5—C4 | 173.09 (14) | Fe—C1—C11—C12 | 168.38 (11) |
C1—Fe—C5—C4 | 119.21 (15) | O1—C11—C12—C16 | 160.95 (15) |
C10—Fe—C5—C4 | −109.99 (12) | C1—C11—C12—C16 | 37.8 (2) |
C2—Fe—C5—C4 | 81.29 (11) | O1—C11—C12—C13 | −20.6 (2) |
C9—Fe—C5—C4 | −71.62 (14) | C1—C11—C12—C13 | −143.73 (15) |
C3—Fe—C5—C4 | 37.36 (11) | C16—C12—C13—C19 | −0.2 (3) |
C6—Fe—C5—C1 | 87.80 (11) | C11—C12—C13—C19 | −178.73 (15) |
C7—Fe—C5—C1 | 53.88 (18) | C16—C12—C13—C14 | −179.16 (16) |
C10—Fe—C5—C1 | 130.80 (10) | C11—C12—C13—C14 | 2.4 (2) |
C4—Fe—C5—C1 | −119.21 (15) | C19—C13—C14—C15 | 164.90 (18) |
C2—Fe—C5—C1 | −37.92 (9) | C12—C13—C14—C15 | −16.2 (2) |
C9—Fe—C5—C1 | 169.17 (10) | C11—O1—C15—C14 | −70.7 (2) |
C3—Fe—C5—C1 | −81.85 (10) | C13—C14—C15—O1 | 48.9 (2) |
C5—Fe—C6—C7 | −151.58 (11) | C13—C12—C16—C17 | 0.0 (3) |
C1—Fe—C6—C7 | −108.22 (12) | C11—C12—C16—C17 | 178.42 (16) |
C10—Fe—C6—C7 | 118.94 (18) | C12—C16—C17—C18 | 0.3 (3) |
C8—Fe—C6—C7 | 37.98 (12) | C16—C17—C18—C19 | −0.2 (3) |
C4—Fe—C6—C7 | 174.88 (13) | C17—C18—C19—C13 | −0.1 (3) |
C2—Fe—C6—C7 | −69.63 (15) | C12—C13—C19—C18 | 0.3 (3) |
C9—Fe—C6—C7 | 81.73 (13) | C14—C13—C19—C18 | 179.21 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14A···Cg1i | 0.97 | 2.85 | 3.627 (2) | 138 |
C18—H18···Cg2ii | 0.93 | 2.88 | 3.660 (2) | 142 |
C18—H18···C7ii | 0.93 | 2.86 | 3.760 (3) | 163 |
C18—H18···C6ii | 0.93 | 3.03 | 3.874 (3) | 151 |
C5—H5···Cg1iii | 0.93 | 3.14 | 3.984 (2) | 152 |
C5—H5···C12iii | 0.93 | 2.98 | 3.840 (2) | 154 |
C5—H5···C13iii | 0.93 | 3.02 | 3.949 (2) | 177 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z+1; (iii) −x+1, −y, −z+2. |
Experimental details
Crystal data | |
Chemical formula | [Fe(C5H5)(C14H13O)] |
Mr | 318.18 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 293 |
a, b, c (Å) | 11.5053 (2), 18.5095 (3), 7.1941 (1) |
β (°) | 106.933 (1) |
V (Å3) | 1465.62 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 1.02 |
Crystal size (mm) | 0.80 × 0.40 × 0.15 |
Data collection | |
Diffractometer | Nonius KappaCCD area-detector diffractometer |
Absorption correction | Multi-scan (DENZO–SMN; Otwinovski & Minor, 1997) |
Tmin, Tmax | 0.630, 0.857 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 16885, 3334, 2662 |
Rint | 0.064 |
(sin θ/λ)max (Å−1) | 0.648 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.030, 0.076, 1.03 |
No. of reflections | 3334 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.25, −0.23 |
Computer programs: COLLECT (Nonius, 2000), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003), SHELXL97.
O1—C11 | 1.4236 (19) | C13—C19 | 1.392 (3) |
O1—C15 | 1.432 (2) | C13—C14 | 1.504 (3) |
C1—C11 | 1.503 (2) | C14—C15 | 1.501 (3) |
C11—C12 | 1.523 (2) | C16—C17 | 1.384 (3) |
C12—C16 | 1.388 (2) | C17—C18 | 1.380 (3) |
C12—C13 | 1.397 (2) | C18—C19 | 1.379 (3) |
C11—O1—C15 | 110.39 (13) | C1—C11—C12 | 112.14 (13) |
C2—C1—C11 | 127.61 (14) | C13—C12—C11 | 119.77 (14) |
C5—C1—C11 | 124.78 (14) | C12—C13—C14 | 120.38 (16) |
O1—C11—C1 | 109.37 (13) | C15—C14—C13 | 111.24 (15) |
O1—C11—C12 | 111.64 (13) | O1—C15—C14 | 110.04 (15) |
D—H···A | D—H | H···A | D···A | D—H···A |
C14—H14A···Cg1i | 0.97 | 2.85 | 3.627 (2) | 138 |
C18—H18···Cg2ii | 0.93 | 2.88 | 3.660 (2) | 142 |
C18—H18···C7ii | 0.93 | 2.86 | 3.760 (3) | 163 |
C18—H18···C6ii | 0.93 | 3.03 | 3.874 (3) | 151 |
C5—H5···Cg1iii | 0.93 | 3.14 | 3.984 (2) | 152 |
C5—H5···C12iii | 0.93 | 2.98 | 3.840 (2) | 154 |
C5—H5···C13iii | 0.93 | 3.02 | 3.949 (2) | 177 |
Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) x+1, y, z+1; (iii) −x+1, −y, −z+2. |
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Optically active ferrocene derivatives are widely employed as chiral ligands in asymmetric reactions, and there is continuing interest in the development of efficient procedures for the preparation of these derivatives in enantiopure form (Gonsalves & Chen, 1995; Bolm et al., 1998; Pioda & Togni, 1998; Perea et al., 1999). Ferrocene derivatives exhibiting centro- and planar chirality are very convenient substrates for biotransformations (Köllner et al., 1998; Richards & Locke, 1998; Schwink & Knochel, 1998; Patti & Nicolosi, 1999; Đaković et al., 2003). In the course of our research on enzyme-catalyzed resolution of centrochiral ferrocene compounds, racemic 2-(α-hydroxyferrocyl)benzenethanol and 1-ferrocenylisochromane, (I), were prepared by reduction of methyl 2-(ferrocenoyl)benzenacetate (Đaković, 2000).
The molecular structure of (I) is the first reported structure to contain an isochromanyl group attached to the ferrocenyl moiety (Fig. 1). Moreover, a survey of the Cambridge Structural Database (Allen, 2002) lists only three structures containing an isochromanyl group at all (Yamato et al., 1984; Unterhalt et al., 1994; Eikawa et al., 1999). The heterocyclic six-membered ring adopts a distorted half-chair conformation, in which atoms O1 and C15 are 0.426 (1) and −0.348 (2) Å from the plane of the other ring atoms (C11/C12/C13/C14); the C11—C12—C13—C14 torsion angle is 2.4 (2)°. The bond lengths in the heterocyclic and fused phenyl rings (Table 1) mostly agree with those in the structures of 1,1'-oxybis(isochromane) (Eikawa et al., 1999) and (S)-1-(phenyl)ethylammonium (S)-isochromane-1-carboxylate (Unterhalt et al., 1994). The exception is the C12—C13 bond length, which is shorter [ca 0.04 Å]in the latter structure. The heterocyclic ring atoms O1, C11 and C15 and the cyclopentadienyl (Cp) ring atom C1 lie in the same plane; the C15—O1—C11—C1 torsion angle is 178.95 (14)°. The dihedral angle between the mean planes of these four atoms and the C1–C5 Cp ring is 47.8 (1)°. Furthermore, the plane of the heterocyclic ring is almost perpendicular to the plane of the C1–C5 ring and parallel to the plane of the fused phenyl ring. The corresponding dihedral angles are 87.3 (1) and 4.0 (1)°.
The exocyclic C2—C1—C11 Cp bond angle is larger than the C5–C1–C11 angle (Table 1). The Cp rings are planar and almost parallel to each other [the dihedral angle is 2.7 (1)°]. The Fe—C distances are in the range 2.034 (2)–2.051 (2) Å for the substituted (C1—C5) and 2.029 (2)–2.049 (2) Å for the unsubstituted (C6—C10) ring, the average values being 2.042 (2) and 2.038 (2) Å, respectively. The C—C bonds are slightly longer in the substituted ring than in the unsubstituted ring [1.410 (3)–1.429 (2) Å versus 1.397 (3)–1.414 (3) Å], and the bond angles in both rings range from 107.52 (15) to 108.33 (18)°.
The geometry of the ferrocenyl moiety agrees well with the structures of ferrocene (Seiler & Dunitz, 1979) and of the ferrocene structures (derivatives?) we have reported previously (Cetina et al., 2002; Cetina et al., 2003). The main conformational difference was observed in the orientation of the Cp rings. In (I), the rings are twisted from the eclipsed conformation by? 19.4 (2)° (average value). The values of the corresponding C—Cg1—Cg2—C pseudo-torsion angles (Cg1 and Cg2 are the centroids of the C1—C5 and C6—C10 rings, respectively), defined by joining two eclipsing Cp C atoms through the ring centroids, range from 19.0 (2) to 19.7 (2)°. The conformation is almost exactly halfway between eclipsed and staggered, as demonstrated by the C1–Cg1–Cg2–C9 torsion angle of 163.4 (1)°. For a staggered conformation, this angle is 180°, and for a fully eclipsed conformation, it is 144°. The centroids of the Cp rings are almost equidistant from the Fe atom. The Fe—Cg1 and Fe—Cg2 distances are 1.647 (1) and 1.650 (1) Å, while the Cg1—Fe—Cg2 angle is 178.2 (1)°.
There are a number of C—H···π interactions (Table 2 and Fig. 2). Atom H14A of the heterocyclic ring is positioned almost perpendicularly above the phenyl-ring centroid (Cg1) of the adjacent molecule. The six relevant H···C distances fall into the narrow range 3.06–3.28 Å, and the H···Cgi distance is significantly shorter than any of the H···C distances. The C—H···π interaction between atom H18 of the phenyl ring and the unsubstituted Cp ring exhibits a completely different geometry. The H18···C7ii distance is shorter than the H···Cgii distance. The second shortest H···C contact is that to atom C6, and the C—H bond points towards the C6—C7 bond of the Cp ring rather than to the ring centroid (Cg2). Similarly, the longest C5—H5···Cg1iii interaction points towards the C12–C13 bond. Both the H5···C12iii and the H5···C13iii contact is shorter than the H···Cgiii distance. The molecules linked by these C—H···π interactions build a three-dimensional framework.