Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106002800/hj1087sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106002800/hj1087IIasup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270106002800/hj1087IIbsup3.hkl |
CCDC references: 603211; 603212
Samples of (IIa) and (IIb) were synthesized by epoxidation of the parent compounds (Ia) and (Ib), respectively, and were recrystallized from a mixture of pentane and tert-butyl methyl ether (10:1). Compound (IIa): m.p. 456.3–457.9 K; 1H (CDCl3): δ 0.77 (3H, s), 1.60 (3H, s), 2.44 (1H, s), 2.73–2.97 (2H, m), 3.00 (1H, s), 3.30–3.40 (1H, m), 4.08–4.17(1H, m), 6.95–6.99 (2H, m), 7.00–7.26 (6H, m); 13C (CDCl3): δ 13.4, 18.5, 29.8, 31.6, 38.0, 44.9, 48.1, 59.7, 60.6, 125.8, 126.3, 126.5, 126.9, 128.1, 128.1, 130.2, 132.2, 134.9, 138.6, 139.2, 140.4, 197.4, 201.0. Compound (IIb): m.p. 425.4–426.3 K; 1H (CDCl3): δ 1.21 (3H, s), 1.34 (3H, s), 2.71–2.95 (2H, m), 2.73 (1H, s), 2.97 (1H, s), 3.41–3.67 (2H, m), 7.0–7.37 (8H, m); 13C (CDCl3): δ 14.6, 16.3, 30.3, 32.2, 37.9, 39.5, 48.8, 60.1, 61.0, 126.1, 126.2, 126.8, 127.2, 128.2, 128.7, 130.2, 131.7, 135.5, 136.9, 138.4, 141.0, 199.0, 199.4.
H atoms bonded to C atoms were placed in geometrically idealized positions, with C—H distances of 0.95–0.98 Å, and refined as riding atoms, with Uiso(H) values of 1.2Ueq(C).
For both compounds, data collection: PROCESS-AUTO (Rigaku Corporation, 1998); cell refinement: PROCESS-AUTO. Data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000) for (IIa); TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000 for (IIb). For both compounds, program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: TEXSAN; software used to prepare material for publication: TEXSAN.
C23H20O3 | Dx = 1.311 Mg m−3 |
Mr = 344.41 | Melting point = 183.1–184.7 K |
Monoclinic, P21/a | Mo Kα radiation, λ = 0.7107 Å |
a = 12.517 (1) Å | Cell parameters from 15836 reflections |
b = 10.206 (1) Å | θ = 2.7–27.5° |
c = 14.704 (2) Å | µ = 0.09 mm−1 |
β = 111.747 (7)° | T = 223 K |
V = 1744.7 (4) Å3 | Platelet, colorless |
Z = 4 | 0.30 × 0.20 × 0.10 mm |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 2584 reflections with F2 > 2σ(F2) |
Detector resolution: 8.00 pixels mm-1 | Rint = 0.081 |
ω scans | θmax = 27.5° |
Absorption correction: multi-scan (Higashi, 1995) | h = −16→16 |
Tmin = 0.974, Tmax = 0.991 | k = −13→13 |
13852 measured reflections | l = −19→19 |
3922 independent reflections |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.086 | w = 1/(σ2(Fo2) + {0.05[Max(Fo2,0) + 2Fc2]/3}2) |
wR(F2) = 0.188 | (Δ/σ)max = 0.007 |
S = 1.96 | Δρmax = 0.60 e Å−3 |
3922 reflections | Δρmin = −0.46 e Å−3 |
235 parameters |
C23H20O3 | V = 1744.7 (4) Å3 |
Mr = 344.41 | Z = 4 |
Monoclinic, P21/a | Mo Kα radiation |
a = 12.517 (1) Å | µ = 0.09 mm−1 |
b = 10.206 (1) Å | T = 223 K |
c = 14.704 (2) Å | 0.30 × 0.20 × 0.10 mm |
β = 111.747 (7)° |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3922 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 2584 reflections with F2 > 2σ(F2) |
Tmin = 0.974, Tmax = 0.991 | Rint = 0.081 |
13852 measured reflections |
R[F2 > 2σ(F2)] = 0.086 | 235 parameters |
wR(F2) = 0.188 | H-atom parameters constrained |
S = 1.96 | Δρmax = 0.60 e Å−3 |
3922 reflections | Δρmin = −0.46 e Å−3 |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
O1 | −0.2400 (2) | −0.4268 (2) | −0.5602 (2) | 0.0620 (8) | |
O2 | −0.3936 (2) | −0.5743 (2) | −0.9365 (2) | 0.0448 (7) | |
O3 | −0.2593 (2) | −0.6545 (2) | −0.7128 (2) | 0.0459 (7) | |
C1 | −0.3681 (3) | −0.6727 (3) | −0.6012 (2) | 0.049 (1) | |
C2 | −0.3369 (2) | −0.5921 (3) | −0.6732 (2) | 0.0338 (8) | |
C3 | −0.3773 (2) | −0.6275 (3) | −0.7771 (2) | 0.0335 (8) | |
C4 | −0.3842 (2) | −0.5312 (3) | −0.8560 (2) | 0.0322 (8) | |
C5 | −0.3721 (2) | −0.3884 (3) | −0.8334 (2) | 0.0295 (7) | |
C6 | −0.3228 (2) | −0.3541 (3) | −0.7235 (2) | 0.0317 (7) | |
C7 | −0.2963 (2) | −0.4533 (3) | −0.6453 (2) | 0.0387 (8) | |
C8 | −0.3285 (2) | −0.3082 (3) | −0.8990 (2) | 0.0409 (9) | |
C9 | −0.4498 (2) | −0.3263 (3) | −0.7858 (2) | 0.0267 (7) | |
C10 | −0.5424 (2) | −0.4046 (2) | −0.7675 (2) | 0.0264 (7) | |
C11 | −0.6123 (2) | −0.4896 (3) | −0.8400 (2) | 0.0317 (7) | |
C12 | −0.7003 (2) | −0.5597 (3) | −0.8267 (3) | 0.0408 (9) | |
C13 | −0.7214 (3) | −0.5423 (3) | −0.7423 (3) | 0.047 (1) | |
C14 | −0.6556 (3) | −0.4545 (3) | −0.6719 (3) | 0.0416 (9) | |
C15 | −0.5666 (2) | −0.3825 (3) | −0.6826 (2) | 0.0325 (8) | |
C16 | −0.5057 (3) | −0.2854 (3) | −0.6012 (2) | 0.0434 (9) | |
C17 | −0.4396 (3) | −0.1678 (3) | −0.6215 (2) | 0.0443 (9) | |
C18 | −0.4885 (2) | −0.1111 (3) | −0.7233 (2) | 0.0357 (8) | |
C19 | −0.5367 (2) | 0.0144 (3) | −0.7406 (3) | 0.0466 (10) | |
C20 | −0.5802 (3) | 0.0676 (3) | −0.8330 (3) | 0.051 (1) | |
C21 | −0.5789 (2) | −0.0046 (3) | −0.9135 (3) | 0.0465 (10) | |
C22 | −0.5340 (2) | −0.1318 (3) | −0.8979 (2) | 0.0371 (8) | |
C23 | −0.4880 (2) | −0.1846 (3) | −0.8041 (2) | 0.0294 (7) | |
H1 | −0.4199 | −0.6239 | −0.5794 | 0.0597* | |
H2 | −0.3012 | −0.6931 | −0.5463 | 0.0597* | |
H3 | −0.4054 | −0.7512 | −0.6313 | 0.0597* | |
H4 | −0.4276 | −0.7015 | −0.7965 | 0.0398* | |
H5 | −0.2743 | −0.2780 | −0.7076 | 0.0381* | |
H6 | −0.3797 | −0.3163 | −0.9660 | 0.0512* | |
H7 | −0.3231 | −0.2178 | −0.8815 | 0.0512* | |
H8 | −0.2541 | −0.3382 | −0.8941 | 0.0512* | |
H9 | −0.5985 | −0.4993 | −0.9005 | 0.0386* | |
H10 | −0.7481 | −0.6196 | −0.8771 | 0.0492* | |
H11 | −0.7834 | −0.5911 | −0.7337 | 0.0552* | |
H12 | −0.6713 | −0.4437 | −0.6127 | 0.0524* | |
H13 | −0.5611 | −0.2492 | −0.5782 | 0.0524* | |
H14 | −0.4506 | −0.3342 | −0.5482 | 0.0524* | |
H15 | −0.4354 | −0.0998 | −0.5751 | 0.0514* | |
H16 | −0.3618 | −0.1960 | −0.6091 | 0.0514* | |
H17 | −0.5381 | 0.0648 | −0.6852 | 0.0566* | |
H18 | −0.6122 | 0.1545 | −0.8428 | 0.0601* | |
H19 | −0.6104 | 0.0315 | −0.9803 | 0.0567* | |
H20 | −0.5353 | −0.1848 | −0.9532 | 0.0455* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.075 (2) | 0.049 (1) | 0.036 (1) | 0.001 (1) | −0.010 (1) | −0.005 (1) |
O2 | 0.058 (1) | 0.043 (1) | 0.038 (1) | 0.004 (1) | 0.023 (1) | −0.005 (1) |
O3 | 0.043 (1) | 0.039 (1) | 0.054 (2) | 0.0074 (9) | 0.016 (1) | 0.002 (1) |
C1 | 0.065 (2) | 0.044 (2) | 0.037 (2) | 0.001 (2) | 0.017 (2) | 0.011 (2) |
C2 | 0.035 (1) | 0.030 (2) | 0.032 (2) | 0.005 (1) | 0.008 (1) | 0.002 (1) |
C3 | 0.032 (1) | 0.026 (1) | 0.042 (2) | −0.002 (1) | 0.013 (1) | 0.000 (1) |
C4 | 0.031 (1) | 0.033 (2) | 0.034 (2) | 0.001 (1) | 0.012 (1) | −0.002 (1) |
C5 | 0.027 (1) | 0.030 (1) | 0.033 (2) | 0.000 (1) | 0.012 (1) | 0.003 (1) |
C6 | 0.024 (1) | 0.023 (1) | 0.045 (2) | −0.003 (1) | 0.010 (1) | −0.003 (1) |
C7 | 0.034 (1) | 0.037 (2) | 0.037 (2) | 0.003 (1) | 0.004 (1) | −0.005 (1) |
C8 | 0.038 (2) | 0.039 (2) | 0.055 (2) | 0.002 (1) | 0.029 (1) | 0.004 (2) |
C9 | 0.025 (1) | 0.024 (1) | 0.030 (2) | −0.0010 (10) | 0.009 (1) | 0.001 (1) |
C10 | 0.028 (1) | 0.021 (1) | 0.030 (2) | 0.0045 (10) | 0.010 (1) | 0.006 (1) |
C11 | 0.030 (1) | 0.031 (2) | 0.032 (2) | 0.000 (1) | 0.010 (1) | 0.000 (1) |
C12 | 0.036 (2) | 0.029 (2) | 0.059 (2) | −0.004 (1) | 0.019 (1) | −0.003 (2) |
C13 | 0.044 (2) | 0.032 (2) | 0.077 (3) | −0.003 (1) | 0.036 (2) | 0.005 (2) |
C14 | 0.054 (2) | 0.034 (2) | 0.052 (2) | 0.006 (1) | 0.037 (2) | 0.010 (2) |
C15 | 0.036 (1) | 0.029 (1) | 0.032 (2) | 0.007 (1) | 0.013 (1) | 0.003 (1) |
C16 | 0.052 (2) | 0.048 (2) | 0.032 (2) | 0.007 (2) | 0.017 (1) | −0.001 (2) |
C17 | 0.048 (2) | 0.043 (2) | 0.041 (2) | −0.003 (1) | 0.015 (1) | −0.020 (2) |
C18 | 0.030 (1) | 0.027 (2) | 0.050 (2) | −0.004 (1) | 0.015 (1) | −0.006 (1) |
C19 | 0.043 (2) | 0.028 (2) | 0.073 (3) | −0.004 (1) | 0.026 (2) | −0.010 (2) |
C20 | 0.041 (2) | 0.027 (2) | 0.091 (3) | 0.004 (1) | 0.032 (2) | 0.008 (2) |
C21 | 0.035 (2) | 0.040 (2) | 0.067 (3) | 0.006 (1) | 0.021 (2) | 0.024 (2) |
C22 | 0.030 (1) | 0.035 (2) | 0.048 (2) | 0.000 (1) | 0.017 (1) | 0.008 (2) |
C23 | 0.023 (1) | 0.025 (1) | 0.041 (2) | −0.002 (1) | 0.014 (1) | 0.002 (1) |
O1—C7 | 1.218 (4) | C11—C12 | 1.388 (4) |
O2—C4 | 1.227 (4) | C11—H9 | 0.971 |
O3—C2 | 1.451 (4) | C12—C13 | 1.372 (6) |
O3—C3 | 1.454 (3) | C12—H10 | 0.976 |
C1—C2 | 1.503 (5) | C13—C14 | 1.386 (4) |
C1—H1 | 0.962 | C13—H11 | 0.969 |
C1—H2 | 0.945 | C14—C15 | 1.391 (5) |
C1—H3 | 0.950 | C14—H12 | 0.966 |
C2—C3 | 1.465 (4) | C15—C16 | 1.524 (4) |
C2—C7 | 1.510 (4) | C16—C17 | 1.548 (5) |
C3—C4 | 1.497 (4) | C16—H13 | 0.951 |
C3—H4 | 0.957 | C16—H14 | 0.965 |
C4—C5 | 1.490 (4) | C17—C18 | 1.507 (4) |
C5—C6 | 1.541 (4) | C17—H15 | 0.961 |
C5—C8 | 1.513 (5) | C17—H16 | 0.966 |
C5—C9 | 1.531 (4) | C18—C19 | 1.399 (4) |
C6—C7 | 1.475 (4) | C18—C23 | 1.408 (5) |
C6—C9 | 1.539 (3) | C19—C20 | 1.375 (6) |
C6—H5 | 0.960 | C19—H17 | 0.970 |
C8—H6 | 0.960 | C20—C21 | 1.399 (6) |
C8—H7 | 0.953 | C20—H18 | 0.961 |
C8—H8 | 0.957 | C21—C22 | 1.400 (4) |
C9—C10 | 1.512 (4) | C21—H19 | 0.984 |
C9—C23 | 1.516 (4) | C22—C23 | 1.391 (4) |
C10—C11 | 1.401 (4) | C22—H20 | 0.971 |
C10—C15 | 1.408 (5) | ||
O1···C1i | 3.436 (4) | O3···C13iii | 3.184 (4) |
O2···O2ii | 3.032 (4) | O3···C19iv | 3.290 (4) |
O2···C11ii | 3.377 (4) | O3···C20iv | 3.446 (5) |
O2···C4ii | 3.452 (3) | O3···C12iii | 3.574 (4) |
O2···C5ii | 3.583 (3) | ||
C2—O3—C3 | 60.6 (2) | C9—C10—C11 | 119.7 (3) |
C2—C1—H1 | 109.6 | C9—C10—C15 | 120.3 (2) |
C2—C1—H2 | 110.0 | C11—C10—C15 | 119.7 (3) |
C2—C1—H3 | 110.1 | C10—C11—C12 | 121.1 (3) |
H1—C1—H2 | 108.9 | C10—C11—H9 | 119.2 |
H1—C1—H3 | 108.4 | C12—C11—H9 | 119.7 |
H2—C1—H3 | 109.8 | C11—C12—C13 | 119.3 (3) |
O3—C2—C1 | 115.4 (2) | C11—C12—H10 | 120.8 |
O3—C2—C3 | 59.8 (2) | C13—C12—H10 | 119.9 |
O3—C2—C7 | 108.3 (2) | C12—C13—C14 | 119.9 (3) |
C1—C2—C3 | 121.4 (2) | C12—C13—H11 | 118.9 |
C1—C2—C7 | 118.1 (3) | C14—C13—H11 | 121.2 |
C3—C2—C7 | 117.8 (3) | C13—C14—C15 | 122.4 (4) |
O3—C3—C2 | 59.6 (2) | C13—C14—H12 | 118.9 |
O3—C3—C4 | 112.5 (2) | C15—C14—H12 | 118.7 |
O3—C3—H4 | 116.2 | C10—C15—C14 | 117.4 (3) |
C2—C3—C4 | 123.0 (2) | C10—C15—C16 | 126.2 (3) |
C2—C3—H4 | 116.0 | C14—C15—C16 | 116.4 (3) |
C4—C3—H4 | 116.4 | C15—C16—C17 | 120.1 (3) |
O2—C4—C3 | 118.0 (3) | C15—C16—H13 | 108.2 |
O2—C4—C5 | 122.1 (3) | C15—C16—H14 | 107.4 |
C3—C4—C5 | 119.8 (3) | C17—C16—H13 | 106.3 |
C4—C5—C6 | 115.1 (2) | C17—C16—H14 | 106.4 |
C4—C5—C8 | 114.7 (3) | H13—C16—H14 | 108.1 |
C4—C5—C9 | 118.5 (3) | C16—C17—C18 | 116.1 (2) |
C6—C5—C8 | 116.5 (2) | C16—C17—H15 | 108.4 |
C6—C5—C9 | 60.1 (2) | C16—C17—H16 | 107.8 |
C8—C5—C9 | 120.5 (2) | C18—C17—H15 | 108.8 |
C5—C6—C7 | 123.3 (2) | C18—C17—H16 | 108.2 |
C5—C6—C9 | 59.6 (2) | H15—C17—H16 | 107.2 |
C5—C6—H5 | 114.3 | C17—C18—C19 | 121.5 (3) |
C7—C6—C9 | 118.4 (2) | C17—C18—C23 | 120.5 (3) |
C7—C6—H5 | 115.2 | C19—C18—C23 | 118.0 (3) |
C9—C6—H5 | 114.6 | C18—C19—C20 | 121.9 (4) |
O1—C7—C2 | 119.7 (3) | C18—C19—H17 | 118.3 |
O1—C7—C6 | 121.8 (3) | C20—C19—H17 | 119.8 |
C2—C7—C6 | 118.4 (2) | C19—C20—C21 | 120.2 (3) |
C5—C8—H6 | 110.3 | C19—C20—H18 | 120.2 |
C5—C8—H7 | 111.0 | C21—C20—H18 | 119.6 |
C5—C8—H8 | 110.4 | C20—C21—C22 | 118.7 (3) |
H6—C8—H7 | 108.4 | C20—C21—H19 | 121.4 |
H6—C8—H8 | 108.1 | C22—C21—H19 | 119.9 |
H7—C8—H8 | 108.6 | C21—C22—C23 | 121.0 (3) |
C5—C9—C6 | 60.3 (2) | C21—C22—H20 | 119.9 |
C5—C9—C10 | 121.4 (2) | C23—C22—H20 | 119.1 |
C5—C9—C23 | 121.8 (3) | C9—C23—C18 | 117.3 (3) |
C6—C9—C10 | 119.2 (2) | C9—C23—C22 | 122.2 (3) |
C6—C9—C23 | 118.0 (2) | C18—C23—C22 | 120.1 (3) |
C10—C9—C23 | 108.9 (2) | ||
O1—C7—C2—O3 | −99.5 (4) | C6—C9—C10—C11 | −114.4 (3) |
O1—C7—C2—C1 | 34.0 (4) | C6—C9—C10—C15 | 72.2 (3) |
O1—C7—C2—C3 | −164.4 (3) | C6—C9—C23—C18 | −68.1 (4) |
O1—C7—C6—C5 | 167.4 (3) | C6—C9—C23—C22 | 119.5 (3) |
O1—C7—C6—C9 | −122.1 (3) | C7—C6—C5—C8 | −142.6 (3) |
O2—C4—C3—O3 | 96.4 (3) | C7—C6—C5—C9 | 105.9 (3) |
O2—C4—C3—C2 | 163.8 (3) | C7—C6—C9—C10 | −2.3 (4) |
O2—C4—C5—C6 | −161.0 (3) | C7—C6—C9—C23 | 133.5 (3) |
O2—C4—C5—C8 | −21.7 (3) | C8—C5—C6—C9 | 111.6 (3) |
O2—C4—C5—C9 | 130.7 (3) | C8—C5—C9—C10 | 147.0 (2) |
O3—C2—C3—C4 | −98.5 (3) | C8—C5—C9—C23 | 1.4 (3) |
O3—C2—C7—C6 | 78.2 (3) | C9—C10—C11—C12 | −177.9 (2) |
O3—C3—C2—C1 | −103.1 (3) | C9—C10—C15—C14 | 177.8 (2) |
O3—C3—C2—C7 | 95.9 (3) | C9—C10—C15—C16 | −1.3 (4) |
O3—C3—C4—C5 | −79.6 (3) | C9—C23—C18—C17 | 7.0 (4) |
C1—C2—O3—C3 | 113.0 (3) | C9—C23—C18—C19 | −172.2 (3) |
C1—C2—C3—C4 | 158.4 (3) | C9—C23—C22—C21 | 173.7 (3) |
C1—C2—C7—C6 | −148.2 (3) | C10—C9—C23—C18 | 71.9 (3) |
C2—O3—C3—C4 | 116.1 (3) | C10—C9—C23—C22 | −100.5 (3) |
C2—C3—C4—C5 | −12.3 (4) | C10—C11—C12—C13 | 1.9 (4) |
C2—C7—C6—C5 | −10.3 (4) | C10—C15—C14—C13 | −1.9 (4) |
C2—C7—C6—C9 | 60.2 (4) | C10—C15—C16—C17 | 21.6 (4) |
C3—O3—C2—C7 | −112.1 (3) | C11—C10—C9—C23 | 106.2 (3) |
C3—C2—C7—C6 | 13.4 (4) | C11—C10—C15—C14 | 4.4 (4) |
C3—C4—C5—C6 | 14.9 (4) | C11—C10—C15—C16 | −174.7 (3) |
C3—C4—C5—C8 | 154.2 (2) | C11—C12—C13—C14 | 0.6 (4) |
C3—C4—C5—C9 | −53.3 (3) | C12—C11—C10—C15 | −4.5 (4) |
C4—C3—C2—C7 | −2.5 (4) | C12—C13—C14—C15 | −0.6 (4) |
C4—C5—C6—C7 | −4.0 (4) | C13—C14—C15—C16 | 177.3 (3) |
C4—C5—C6—C9 | −109.8 (3) | C14—C15—C16—C17 | −157.5 (3) |
C4—C5—C9—C6 | 104.2 (3) | C15—C10—C9—C23 | −67.2 (3) |
C4—C5—C9—C10 | −3.8 (3) | C15—C16—C17—C18 | 33.1 (4) |
C4—C5—C9—C23 | −149.4 (2) | C16—C17—C18—C19 | 112.2 (3) |
C5—C6—C9—C10 | 111.7 (3) | C16—C17—C18—C23 | −67.0 (4) |
C5—C6—C9—C23 | −112.5 (3) | C17—C18—C19—C20 | 179.1 (3) |
C5—C9—C6—C7 | −114.0 (3) | C17—C18—C23—C22 | 179.6 (3) |
C5—C9—C10—C11 | −43.3 (3) | C18—C19—C20—C21 | 1.0 (5) |
C5—C9—C10—C15 | 143.3 (2) | C18—C23—C22—C21 | 1.6 (4) |
C5—C9—C23—C18 | −138.8 (3) | C19—C18—C23—C22 | 0.3 (4) |
C5—C9—C23—C22 | 48.9 (3) | C19—C20—C21—C22 | 0.8 (5) |
C6—C5—C9—C10 | −108.0 (3) | C20—C19—C18—C23 | −1.6 (5) |
C6—C5—C9—C23 | 106.4 (2) | C20—C21—C22—C23 | −2.1 (4) |
C6—C9—C5—C8 | −105.0 (2) | C20—C21—C22—C23 | −2.1 (4) |
Symmetry codes: (i) −x−1/2, y+1/2, −z−1; (ii) −x−1, −y−1, −z−2; (iii) x+1/2, −y−3/2, z; (iv) x+1/2, −y−1/2, z. |
C23H20O3 | Melting point = 152.2–153.1 K |
Mr = 344.41 | Mo Kα radiation, λ = 0.7107 Å |
Orthorhombic, Pbca | Cell parameters from 38732 reflections |
a = 9.4653 (3) Å | θ = 1.6–27.5° |
b = 14.6974 (4) Å | µ = 0.09 mm−1 |
c = 25.3890 (9) Å | T = 213 K |
V = 3532.0 (2) Å3 | Platelet, colorless |
Z = 8 | 0.30 × 0.30 × 0.10 mm |
Dx = 1.295 Mg m−3 |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 2670 reflections with F2 > 2.0σ(F2) |
Detector resolution: 8.00 pixels mm-1 | Rint = 0.085 |
ω scans | θmax = 27.4° |
Absorption correction: multi-scan (Higashi, 1995) | h = −12→12 |
Tmin = 0.974, Tmax = 0.992 | k = −19→16 |
26252 measured reflections | l = −32→32 |
3955 independent reflections |
Refinement on F2 | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.077 | w = 1/[σ2(Fo2) + (0.05000(Max(Fo2,0) + 2Fc2)/3)2] |
wR(F2) = 0.176 | (Δ/σ)max = 0.008 |
S = 1.90 | Δρmax = 0.54 e Å−3 |
3955 reflections | Δρmin = −0.45 e Å−3 |
235 parameters |
C23H20O3 | V = 3532.0 (2) Å3 |
Mr = 344.41 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 9.4653 (3) Å | µ = 0.09 mm−1 |
b = 14.6974 (4) Å | T = 213 K |
c = 25.3890 (9) Å | 0.30 × 0.30 × 0.10 mm |
Rigaku R-AXIS RAPID imaging-plate diffractometer | 3955 independent reflections |
Absorption correction: multi-scan (Higashi, 1995) | 2670 reflections with F2 > 2.0σ(F2) |
Tmin = 0.974, Tmax = 0.992 | Rint = 0.085 |
26252 measured reflections |
R[F2 > 2σ(F2)] = 0.077 | 235 parameters |
wR(F2) = 0.176 | H-atom parameters constrained |
S = 1.90 | Δρmax = 0.54 e Å−3 |
3955 reflections | Δρmin = −0.45 e Å−3 |
Refinement. Refinement using reflections with F2 > −10.0 σ(F2). The weighted R-factor (wR) and goodness of fit (S) are based on F2. R-factor (gt) are based on F. The threshold expression of F2 > 2.0 σ(F2) is used only for calculating R-factor (gt). |
x | y | z | Uiso*/Ueq | ||
O1 | 0.6459 (2) | 0.0325 (1) | 0.04870 (8) | 0.0353 (6) | |
O2 | 0.3140 (2) | −0.0376 (1) | 0.21843 (8) | 0.0312 (5) | |
O3 | 0.6056 (2) | −0.0913 (1) | 0.15553 (8) | 0.0319 (5) | |
C1 | 0.7844 (3) | 0.0335 (2) | 0.1481 (1) | 0.0372 (9) | |
C2 | 0.6357 (3) | 0.0025 (2) | 0.1403 (1) | 0.0246 (7) | |
C3 | 0.5413 (3) | −0.0170 (2) | 0.1847 (1) | 0.0246 (7) | |
C4 | 0.3845 (3) | −0.0178 (2) | 0.1799 (1) | 0.0224 (7) | |
C5 | 0.3176 (3) | −0.0019 (1) | 0.1273 (1) | 0.0200 (6) | |
C6 | 0.4138 (3) | 0.0210 (2) | 0.0821 (1) | 0.0198 (6) | |
C7 | 0.5697 (3) | 0.0209 (2) | 0.0868 (1) | 0.0243 (7) | |
C8 | 0.1849 (3) | −0.0564 (2) | 0.1168 (1) | 0.0302 (8) | |
C9 | 0.3270 (2) | 0.0978 (2) | 0.1068 (1) | 0.0176 (6) | |
C10 | 0.4003 (3) | 0.1686 (1) | 0.1406 (1) | 0.0178 (6) | |
C11 | 0.5259 (3) | 0.2098 (2) | 0.1254 (1) | 0.0226 (7) | |
C12 | 0.5885 (3) | 0.2760 (2) | 0.1563 (1) | 0.0277 (7) | |
C13 | 0.5242 (3) | 0.3032 (2) | 0.2025 (1) | 0.0311 (8) | |
C14 | 0.3967 (3) | 0.2648 (2) | 0.2172 (1) | 0.0268 (7) | |
C15 | 0.3327 (3) | 0.1977 (2) | 0.1867 (1) | 0.0216 (6) | |
C16 | 0.1862 (3) | 0.1642 (2) | 0.1985 (1) | 0.0253 (7) | |
C17 | 0.0798 (3) | 0.2058 (2) | 0.1608 (1) | 0.0262 (7) | |
C18 | 0.0918 (3) | 0.1841 (2) | 0.1023 (1) | 0.0237 (7) | |
C19 | −0.0192 (3) | 0.2169 (2) | 0.0709 (1) | 0.0365 (9) | |
C20 | −0.0256 (3) | 0.2029 (2) | 0.0175 (1) | 0.0426 (9) | |
C21 | 0.0826 (4) | 0.1559 (2) | −0.0072 (1) | 0.0377 (9) | |
C22 | 0.1952 (3) | 0.1237 (2) | 0.0223 (1) | 0.0264 (7) | |
C23 | 0.2013 (3) | 0.1354 (2) | 0.0770 (1) | 0.0204 (6) | |
H1 | 0.7937 | 0.0955 | 0.1372 | 0.0469* | |
H2 | 0.8098 | 0.0290 | 0.1843 | 0.0469* | |
H3 | 0.8477 | −0.0028 | 0.1278 | 0.0469* | |
H4 | 0.5789 | −0.0051 | 0.2194 | 0.0297* | |
H5 | 0.3796 | 0.0011 | 0.0484 | 0.0231* | |
H6 | 0.1151 | −0.0415 | 0.1426 | 0.0374* | |
H7 | 0.1493 | −0.0428 | 0.0829 | 0.0374* | |
H8 | 0.2050 | −0.1198 | 0.1191 | 0.0374* | |
H9 | 0.5695 | 0.1914 | 0.0925 | 0.0275* | |
H10 | 0.6768 | 0.3032 | 0.1456 | 0.0337* | |
H11 | 0.5672 | 0.3484 | 0.2244 | 0.0380* | |
H12 | 0.3506 | 0.2849 | 0.2495 | 0.0344* | |
H13 | 0.1619 | 0.1807 | 0.2340 | 0.0305* | |
H14 | 0.1831 | 0.0996 | 0.1956 | 0.0305* | |
H15 | 0.0863 | 0.2703 | 0.1643 | 0.0304* | |
H16 | −0.0123 | 0.1870 | 0.1719 | 0.0304* | |
H17 | −0.0948 | 0.2493 | 0.0881 | 0.0438* | |
H18 | −0.1042 | 0.2259 | −0.0029 | 0.0500* | |
H19 | 0.0787 | 0.1452 | −0.0441 | 0.0435* | |
H20 | 0.2708 | 0.0922 | 0.0045 | 0.0321* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.027 (1) | 0.045 (1) | 0.033 (1) | −0.0003 (9) | 0.009 (1) | −0.0073 (10) |
O2 | 0.033 (1) | 0.0295 (10) | 0.031 (1) | 0.0044 (8) | 0.004 (1) | 0.0102 (9) |
O3 | 0.0249 (10) | 0.0199 (8) | 0.051 (1) | 0.0030 (7) | −0.001 (1) | 0.0028 (9) |
C1 | 0.024 (1) | 0.038 (2) | 0.050 (2) | −0.003 (1) | −0.009 (2) | 0.006 (1) |
C2 | 0.020 (1) | 0.016 (1) | 0.038 (2) | 0.0022 (10) | −0.005 (1) | −0.001 (1) |
C3 | 0.026 (1) | 0.022 (1) | 0.025 (2) | 0.001 (1) | −0.004 (1) | 0.004 (1) |
C4 | 0.027 (1) | 0.015 (1) | 0.025 (2) | 0.0009 (10) | 0.000 (1) | 0.002 (1) |
C5 | 0.019 (1) | 0.016 (1) | 0.026 (2) | −0.0012 (9) | −0.001 (1) | 0.000 (1) |
C6 | 0.021 (1) | 0.020 (1) | 0.018 (1) | 0.0009 (10) | −0.002 (1) | −0.002 (1) |
C7 | 0.024 (1) | 0.022 (1) | 0.027 (2) | 0.004 (1) | 0.003 (1) | −0.004 (1) |
C8 | 0.026 (1) | 0.022 (1) | 0.043 (2) | −0.005 (1) | −0.006 (1) | 0.002 (1) |
C9 | 0.016 (1) | 0.019 (1) | 0.017 (1) | −0.0006 (9) | 0.002 (1) | −0.001 (1) |
C10 | 0.018 (1) | 0.016 (1) | 0.020 (1) | 0.0022 (9) | −0.003 (1) | 0.0019 (10) |
C11 | 0.022 (1) | 0.020 (1) | 0.026 (2) | 0.0032 (10) | 0.000 (1) | 0.003 (1) |
C12 | 0.024 (1) | 0.019 (1) | 0.041 (2) | −0.003 (1) | −0.008 (1) | 0.002 (1) |
C13 | 0.037 (2) | 0.019 (1) | 0.037 (2) | 0.003 (1) | −0.020 (2) | −0.006 (1) |
C14 | 0.035 (2) | 0.022 (1) | 0.023 (1) | 0.010 (1) | −0.006 (1) | −0.003 (1) |
C15 | 0.023 (1) | 0.020 (1) | 0.021 (1) | 0.0075 (10) | −0.003 (1) | 0.000 (1) |
C16 | 0.028 (1) | 0.022 (1) | 0.025 (2) | 0.006 (1) | 0.006 (1) | −0.004 (1) |
C17 | 0.019 (1) | 0.026 (1) | 0.034 (2) | 0.002 (1) | 0.003 (1) | −0.005 (1) |
C18 | 0.020 (1) | 0.020 (1) | 0.032 (2) | 0.0015 (10) | −0.001 (1) | 0.002 (1) |
C19 | 0.027 (1) | 0.034 (1) | 0.048 (2) | 0.010 (1) | 0.000 (2) | 0.003 (1) |
C20 | 0.036 (2) | 0.045 (2) | 0.047 (2) | 0.012 (1) | −0.013 (2) | 0.010 (2) |
C21 | 0.045 (2) | 0.040 (2) | 0.028 (2) | 0.006 (1) | −0.011 (2) | 0.005 (1) |
C22 | 0.025 (1) | 0.027 (1) | 0.027 (2) | 0.004 (1) | −0.002 (1) | 0.001 (1) |
C23 | 0.021 (1) | 0.016 (1) | 0.025 (2) | −0.0012 (9) | −0.003 (1) | 0.001 (1) |
O1—C7 | 1.218 (4) | C11—C12 | 1.384 (4) |
O2—C4 | 1.220 (3) | C11—H9 | 0.970 |
O3—C2 | 1.460 (3) | C12—C13 | 1.379 (4) |
O3—C3 | 1.452 (3) | C12—H10 | 0.966 |
C1—C2 | 1.492 (4) | C13—C14 | 1.384 (4) |
C1—H1 | 0.957 | C13—H11 | 0.958 |
C1—H2 | 0.952 | C14—C15 | 1.393 (4) |
C1—H3 | 0.954 | C14—H12 | 0.975 |
C2—C3 | 1.466 (4) | C15—C16 | 1.502 (4) |
C2—C7 | 1.521 (4) | C16—C17 | 1.518 (4) |
C3—C4 | 1.490 (4) | C16—H13 | 0.961 |
C3—H4 | 0.967 | C16—H14 | 0.952 |
C4—C5 | 1.495 (4) | C17—C18 | 1.524 (4) |
C5—C6 | 1.503 (4) | C17—H15 | 0.954 |
C5—C8 | 1.514 (4) | C17—H16 | 0.957 |
C5—C9 | 1.557 (3) | C18—C19 | 1.404 (4) |
C6—C7 | 1.480 (4) | C18—C23 | 1.413 (4) |
C6—C9 | 1.530 (3) | C19—C20 | 1.374 (5) |
C6—H5 | 0.961 | C19—H17 | 0.963 |
C8—H6 | 0.956 | C20—C21 | 1.385 (5) |
C8—H7 | 0.946 | C20—H18 | 0.966 |
C8—H8 | 0.954 | C21—C22 | 1.385 (4) |
C9—C10 | 1.517 (3) | C21—H19 | 0.950 |
C9—C23 | 1.515 (4) | C22—C23 | 1.401 (4) |
C10—C11 | 1.390 (4) | C22—H20 | 0.965 |
C10—C15 | 1.400 (4) | ||
O3···C17i | 3.462 (3) | O2···C14i | 3.523 (3) |
O3···C12ii | 3.491 (3) | O2···C1v | 3.557 (4) |
O1···C22iii | 3.284 (3) | O2···C3v | 3.578 (3) |
O1···C6iii | 3.460 (3) | C8···C13i | 3.593 (4) |
O2···C13iv | 3.444 (3) | C13···C16vi | 3.585 (4) |
C2—O3—C3 | 60.4 (2) | C9—C10—C11 | 122.1 (2) |
C2—C1—H1 | 109.8 | C9—C10—C15 | 118.3 (2) |
C2—C1—H2 | 110.2 | C11—C10—C15 | 119.4 (2) |
C2—C1—H3 | 110.5 | C10—C11—C12 | 120.9 (2) |
H1—C1—H2 | 108.7 | C10—C11—H9 | 118.9 |
H1—C1—H3 | 108.5 | C12—C11—H9 | 120.1 |
H2—C1—H3 | 109.0 | C11—C12—C13 | 119.8 (2) |
O3—C2—C1 | 115.9 (2) | C11—C12—H10 | 120.1 |
O3—C2—C3 | 59.5 (2) | C13—C12—H10 | 120.1 |
O3—C2—C7 | 108.9 (2) | C12—C13—C14 | 119.8 (3) |
C1—C2—C3 | 122.2 (3) | C12—C13—H11 | 120.6 |
C1—C2—C7 | 116.9 (2) | C14—C13—H11 | 119.7 |
C3—C2—C7 | 118.1 (2) | C13—C14—C15 | 121.2 (3) |
O3—C3—C2 | 60.1 (2) | C13—C14—H12 | 119.6 |
O3—C3—C4 | 111.7 (2) | C15—C14—H12 | 119.2 |
O3—C3—H4 | 116.5 | C10—C15—C14 | 118.8 (2) |
C2—C3—C4 | 123.1 (2) | C10—C15—C16 | 119.2 (2) |
C2—C3—H4 | 116.1 | C14—C15—C16 | 121.6 (2) |
C4—C3—H4 | 116.3 | C15—C16—C17 | 110.8 (2) |
O2—C4—C3 | 118.8 (2) | C15—C16—H13 | 108.9 |
O2—C4—C5 | 121.5 (2) | C15—C16—H14 | 109.9 |
C3—C4—C5 | 119.6 (2) | C17—C16—H13 | 109.3 |
C4—C5—C6 | 117.4 (2) | C17—C16—H14 | 109.5 |
C4—C5—C8 | 115.2 (2) | H13—C16—H14 | 108.4 |
C4—C5—C9 | 114.9 (2) | C16—C17—C18 | 118.7 (2) |
C6—C5—C8 | 119.1 (2) | C16—C17—H15 | 107.4 |
C6—C5—C9 | 60.0 (2) | C16—C17—H16 | 107.6 |
C8—C5—C9 | 119.1 (2) | C18—C17—H15 | 107.2 |
C5—C6—C7 | 122.9 (2) | C18—C17—H16 | 107.1 |
C5—C6—C9 | 61.8 (2) | H15—C17—H16 | 108.5 |
C5—C6—H5 | 114.1 | C17—C18—C19 | 115.2 (2) |
C7—C6—C9 | 120.2 (2) | C17—C18—C23 | 127.1 (2) |
C7—C6—H5 | 114.0 | C19—C18—C23 | 117.7 (3) |
C9—C6—H5 | 114.1 | C18—C19—C20 | 122.8 (3) |
O1—C7—C2 | 119.4 (2) | C18—C19—H17 | 118.0 |
O1—C7—C6 | 121.8 (3) | C20—C19—H17 | 119.2 |
C2—C7—C6 | 118.8 (2) | C19—C20—C21 | 119.2 (3) |
C5—C8—H6 | 109.4 | C19—C20—H18 | 120.7 |
C5—C8—H7 | 110.1 | C21—C20—H18 | 120.1 |
C5—C8—H8 | 109.9 | C20—C21—C22 | 119.7 (3) |
H6—C8—H7 | 109.3 | C20—C21—H19 | 120.0 |
H6—C8—H8 | 108.6 | C22—C21—H19 | 120.3 |
H7—C8—H8 | 109.5 | C21—C22—C23 | 121.7 (3) |
C5—C9—C6 | 58.2 (2) | C21—C22—H20 | 118.8 |
C5—C9—C10 | 118.8 (2) | C23—C22—H20 | 119.6 |
C5—C9—C23 | 117.7 (2) | C9—C23—C18 | 122.3 (2) |
C6—C9—C10 | 119.5 (2) | C9—C23—C22 | 118.8 (2) |
C6—C9—C23 | 119.1 (2) | C18—C23—C22 | 118.8 (2) |
C10—C9—C23 | 113.0 (2) | ||
O3—C2—C3—C4 | −97.7 (3) | C6—C9—C10—C11 | 45.7 (3) |
O3—C2—C7—O1 | −111.3 (3) | C6—C9—C10—C15 | −139.1 (2) |
O3—C2—C7—C6 | 66.7 (3) | C6—C9—C23—C18 | 159.8 (2) |
O3—C3—C2—C1 | −103.2 (3) | C6—C9—C23—C22 | −21.9 (3) |
O3—C3—C2—C7 | 96.4 (2) | C7—C6—C5—C8 | −141.8 (2) |
O3—C3—C4—O2 | 110.2 (3) | C7—C6—C5—C9 | 109.5 (2) |
O3—C3—C4—C5 | −65.0 (3) | C7—C6—C9—C10 | −6.0 (3) |
O1—C7—C2—C1 | 22.4 (3) | C7—C6—C9—C23 | 140.1 (2) |
O1—C7—C2—C3 | −176.1 (2) | C8—C5—C6—C9 | 108.7 (2) |
O1—C7—C6—C5 | 174.1 (2) | C8—C5—C9—C10 | 142.5 (2) |
O1—C7—C6—C9 | −111.9 (3) | C8—C5—C9—C23 | −0.1 (4) |
O2—C4—C3—C2 | 177.8 (2) | C9—C10—C11—C12 | 178.2 (2) |
O2—C4—C5—C6 | −179.3 (2) | C9—C10—C15—C14 | −178.0 (2) |
O2—C4—C5—C8 | −31.1 (3) | C9—C10—C15—C16 | −5.2 (3) |
O2—C4—C5—C9 | 113.1 (3) | C9—C23—C18—C17 | −0.5 (4) |
C1—C2—O3—C3 | 113.7 (3) | C9—C23—C18—C19 | 179.3 (2) |
C1—C2—C3—C4 | 159.1 (2) | C9—C23—C22—C21 | 179.5 (2) |
C1—C2—C7—C6 | −159.6 (2) | C10—C9—C23—C18 | −52.1 (3) |
C2—O3—C3—C4 | 116.7 (3) | C10—C9—C23—C22 | 126.2 (2) |
C2—C3—C4—C5 | 2.6 (3) | C10—C11—C12—C13 | −1.3 (4) |
C2—C7—C6—C5 | −3.9 (3) | C10—C15—C14—C13 | 0.6 (4) |
C2—C7—C6—C9 | 70.1 (3) | C10—C15—C16—C17 | −70.4 (3) |
C3—O3—C2—C7 | −112.1 (2) | C11—C10—C9—C23 | −102.3 (3) |
C3—C2—C7—C6 | 1.9 (3) | C11—C10—C15—C14 | −2.7 (4) |
C3—C4—C5—C6 | −4.3 (3) | C11—C10—C15—C16 | 170.1 (2) |
C3—C4—C5—C8 | 143.9 (2) | C11—C12—C13—C14 | −0.8 (4) |
C3—C4—C5—C9 | −71.9 (3) | C12—C11—C10—C15 | 3.1 (4) |
C4—C3—C2—C7 | −1.3 (3) | C12—C13—C14—C15 | 1.1 (4) |
C4—C5—C6—C7 | 5.1 (3) | C13—C14—C15—C16 | −172.0 (2) |
C4—C5—C6—C9 | −104.4 (2) | C14—C15—C16—C17 | 102.2 (3) |
C4—C5—C9—C6 | 108.5 (2) | C15—C10—C9—C23 | 72.9 (3) |
C4—C5—C9—C10 | −0.2 (3) | C15—C16—C17—C18 | 63.6 (3) |
C4—C5—C9—C23 | −142.8 (2) | C16—C17—C18—C19 | 173.3 (2) |
C5—C6—C9—C10 | 107.6 (2) | C16—C17—C18—C23 | −6.9 (4) |
C5—C6—C9—C23 | −106.4 (2) | C17—C18—C19—C20 | −179.6 (3) |
C5—C9—C6—C7 | −113.6 (3) | C17—C18—C23—C22 | −178.8 (2) |
C5—C9—C10—C11 | 113.4 (3) | C18—C19—C20—C21 | −1.2 (5) |
C5—C9—C10—C15 | −71.4 (3) | C18—C23—C22—C21 | −2.2 (4) |
C5—C9—C23—C18 | 92.6 (3) | C19—C18—C23—C22 | 1.0 (3) |
C5—C9—C23—C22 | −89.1 (3) | C19—C20—C21—C22 | 0.1 (4) |
C6—C5—C9—C10 | −108.7 (2) | C20—C19—C18—C23 | 0.6 (4) |
C6—C5—C9—C23 | 108.7 (2) | C20—C21—C22—C23 | 1.6 (4) |
C6—C9—C5—C8 | −108.8 (3) | C20—C21—C22—C23 | 1.6 (4) |
Symmetry codes: (i) −x+1/2, y−1/2, z; (ii) −x+3/2, y−1/2, z; (iii) −x+1, −y, −z; (iv) −x+1, y−1/2, −z+1/2; (v) x−1/2, y, −z+1/2; (vi) x+1/2, y, −z+1/2. |
Experimental details
(IIa) | (IIb) | |
Crystal data | ||
Chemical formula | C23H20O3 | C23H20O3 |
Mr | 344.41 | 344.41 |
Crystal system, space group | Monoclinic, P21/a | Orthorhombic, Pbca |
Temperature (K) | 223 | 213 |
a, b, c (Å) | 12.517 (1), 10.206 (1), 14.704 (2) | 9.4653 (3), 14.6974 (4), 25.3890 (9) |
α, β, γ (°) | 90, 111.747 (7), 90 | 90, 90, 90 |
V (Å3) | 1744.7 (4) | 3532.0 (2) |
Z | 4 | 8 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.09 | 0.09 |
Crystal size (mm) | 0.30 × 0.20 × 0.10 | 0.30 × 0.30 × 0.10 |
Data collection | ||
Diffractometer | Rigaku R-AXIS RAPID imaging-plate diffractometer | Rigaku R-AXIS RAPID imaging-plate diffractometer |
Absorption correction | Multi-scan (Higashi, 1995) | Multi-scan (Higashi, 1995) |
Tmin, Tmax | 0.974, 0.991 | 0.974, 0.992 |
No. of measured, independent and observed reflections | 13852, 3922, 2584 [F2 > 2σ(F2)] | 26252, 3955, 2670 [F2 > 2.0σ(F2)] |
Rint | 0.081 | 0.085 |
(sin θ/λ)max (Å−1) | 0.649 | 0.648 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.086, 0.188, 1.96 | 0.077, 0.176, 1.90 |
No. of reflections | 3922 | 3955 |
No. of parameters | 235 | 235 |
No. of restraints | ? | ? |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.60, −0.46 | 0.54, −0.45 |
Computer programs: PROCESS-AUTO (Rigaku Corporation, 1998), PROCESS-AUTO, TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000), TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 2000, SIR92 (Altomare et al., 1994), TEXSAN.
O1—C7 | 1.218 (4) | C9—C10 | 1.512 (4) |
O2—C4 | 1.227 (4) | C9—C23 | 1.516 (4) |
O3—C2 | 1.451 (4) | C10—C15 | 1.408 (5) |
O3—C3 | 1.454 (3) | C15—C16 | 1.524 (4) |
C2—C3 | 1.465 (4) | C16—C17 | 1.548 (5) |
C5—C6 | 1.541 (4) | C17—C18 | 1.507 (4) |
C5—C9 | 1.531 (4) | C18—C23 | 1.408 (5) |
C6—C9 | 1.539 (3) | ||
C10—C9—C23 | 108.9 (2) | ||
O1—C7—C2—O3 | −99.5 (4) | C15—C16—C17—C18 | 33.1 (4) |
O2—C4—C3—C2 | 163.8 (3) |
O1—C7 | 1.218 (4) | C9—C10 | 1.517 (3) |
O2—C4 | 1.220 (3) | C9—C23 | 1.515 (4) |
O3—C2 | 1.460 (3) | C10—C15 | 1.400 (4) |
O3—C3 | 1.452 (3) | C15—C16 | 1.502 (4) |
C2—C3 | 1.466 (4) | C16—C17 | 1.518 (4) |
C5—C6 | 1.503 (4) | C17—C18 | 1.524 (4) |
C5—C9 | 1.557 (3) | C18—C23 | 1.413 (4) |
C6—C9 | 1.530 (3) | ||
C10—C9—C23 | 113.0 (2) | ||
O1—C7—C2—C3 | −176.1 (2) | C15—C16—C17—C18 | 63.6 (3) |
O2—C4—C3—C2 | 177.8 (2) |
Conformationally, 10,11-dihydro-5H-dibenzo[a,d]cycloheptene and its derivatives have received considerable pharmacological attention in view of their potential as a suitable subunit for drug-receptor concave–convex interaction (Burger, 1983). In our previous paper, we reported that the reaction of 5-diazo-10,11-dihydro-5H-dibenzo[a,d]cycloheptene and 2,5-dimethyl-1, 4-benzoquinone gave the corresponding spirohomobenzoquinone (Ia) via the conformationally locked nitrogen release of the primary adduct pyrazoline (Oshima & Nagai, 1994). Compound (Ia) was found to tranform to the more stable conformer (Ib) at 373 K by way of a complete one-way conformational inversion of the spiro-linked 10,11-dihydro-5H-dibenzo[a,d]cycloheptene moiety (Oshima et al. 1999). We also found that the epoxidation of these conformers (Ia) and (Ib) proceeded without any conformational inversion to give the corresponding epoxides (IIa) and (IIb), respectively, but that thermal equilibration was attained at 373 K in CDCl3 in preference of (IIb) (96%, by 1H NMR) (Asahara, Koizumi & Oshima, unpublished results).
In this paper, we describe the conformational details of these two isomers, (IIa) and (IIb), as determined by X-ray crystallography and compare them with the parent unepoxidized conformers (Ia) and (Ib).
As shown in Fig. 1(a), the dibenzo-fused cycloheptene ring in (IIa) adopts a fairly twisted boat conformation, folding opposite to the cyclopropane CH3 substituent in analogy with (Ia), but the dihedral angle [θ = 33.1 (4)°] of the –CH2—CH2– bridge and the intramolecular bond angle [ω =108.9 (2)°] centered at the spiro-C atom are larger than the corresponding values for (Ia) [27.3 (3) and 107.8 (2)°, respectively]. On the other hand, as shown in Fig. 1(b), the conformationally inverted (IIb) adopts a more highly twisted boat conformation, with θ = 63.6 (3)° and ω = 113 (2)°; the corresponding angles for (Ib) are 55.5 (9) and 111.3 (7)°. It was also found that ω is well correlated with θ, probably because of the constrained dibenzo fusion, i.e. ω = 0.133θ + 104 (n = 4 and R = 0.99, where n and R are the number of data points and the correlation coefficient, respectively).
We also compared these angles θ and ω with the corresponding crystalline values [57.9 (2) and 114.6 (2)°] for the least strained pristine 10,11-dihydro-5H-dibenzo[a,d]cycloheptene, (III) (Reboul & Cristau, 1981). The less stable conformers (Ia) and (IIa) possess the considerably smaller θ values than the ideal gauche angle, while the stable isomers (Ib) and (IIb) as well as (III) adopt substantially the gauche conformations for the –CH2—CH2– bridge.
A perusal of the X-ray structure of (IIa) indicates that several atoms of the dibenzo-fused seven-membered ring occupy crowded positions almost touching the underlying quinone component, as represented by the very short spatial distances between C8 and H20 (2.72 Å), O1 and H16 (2.75 Å), and O1 and H14 (2.87 Å). These unfavorable non-bonding interactions may be taken as a driving force for the conformational isomerization. However, such a van der Waals contact was also observed for the stable (IIb), in particular, between the ethano-bridge H14 atom and the facing carbonyl O2 atom (2.44 Å), appreciably raising the strain energy of (IIb).
With respect to the structure of the quinone frame, (IIb) is especially characterized by being almost planar, as shown by the dihedral angles of 177.8 (2) and −176.1 (2)° for the bond linkages O2—C4—C3—C2 and O1—C7—C2—C3, respectively, whereas the other conformers (Ia), (Ib) and (IIa) adopt slightly folded (12–22°) boat conformations, as indicated by the corresponding angles of 157.7 (3) and −163.5 (3)° for (Ia), 164.0 (14) and −168.2 (13)° for (Ib), and 163.8 (3) and −164.4 (3)° for (IIa), respectively. Of further interest is the fact that the C atoms of the oxirane rings of (IIa) and (IIb) are almost planar, as indicated by the angles of 355° or more when we add the three angles made by the substituents of the oxirane ring and another carbon center. Such a geometrical planarity of oxirane C atoms is commonly known for most of the oxirane derivatives compiled in the Cambridge Structural Database (Version 5.22 of January 2002; Allen, 2002) (Oki et al., 2003).