Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103027859/na1630sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027859/na1630Isup2.hkl | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103027859/na1630IIsup3.hkl |
CCDC references: 233122; 233123
Compound (I) was obtained as reported previously (Barreira Fontecha et al., 2002) and recrystallized from methanol. Compound (II) was obtained from 5,5'-di-tert-butyl-2,2'-dihydroxy-3,3'-methanediyldibenzyl alcohol and cyclohexanone in the presence of p-toluenesulfonic acid. The compound was recrystallized from acetone (m.p. 427.5–429 K). Spectroscopic analysis, 1H NMR (300 MHz, CDCl3, δ, p.p.m.): 1.22 (s, 18H), 1.36–1.50 (m, 2H), 1.54–1.64 (m, 4H), 1.69–1.79 (m, 2H), 1.80–1.90 (m, 2H), 3.89 (s, 2H), 4.82 (s, 2H), 6.77 (d, J = 1.8 Hz, 2H), 7.08 (d, J = 1.8 Hz, 2H).
The hydroxy H atom in (I) was found in a difference Fourier map and introduced as a riding atom, with an isotropic displacement parameter equal to 1.2 times that of the parent atom. All other H atoms in both compounds were introduced at calculated positions as riding atoms, with C—H bond lengths of 0.93 (CH), 0.97 (CH2) and 0.96 Å (CH3) and an isotropic displacement parameter equal to 1.2 (CH and CH2) or 1.5 (CH3) times that of the parent atom.
For both compounds, data collection: KappaCCD Server Software (Nonius, 1998); cell refinement: DENZO–SMN (Otwinowski & Minor, 1997). Data reduction: DENZO–SMN for (I); DENZO–SMN (Otwinowski & Minor, 1997) for (II). For both compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1999); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2000).
C23H28O4 | Dx = 1.246 Mg m−3 |
Mr = 368.45 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I41/a | Cell parameters from 15112 reflections |
Hall symbol: -I 4ad | θ = 2.8–25.7° |
a = 12.7655 (5) Å | µ = 0.08 mm−1 |
c = 24.1122 (11) Å | T = 100 K |
V = 3929.3 (3) Å3 | Irregular, colourless |
Z = 8 | 0.40 × 0.35 × 0.30 mm |
F(000) = 1584 |
Nonius KappaCCD diffractometer | 1437 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.066 |
Graphite monochromator | θmax = 25.7°, θmin = 2.8° |
ϕ scans | h = 0→15 |
15112 measured reflections | k = −10→11 |
1874 independent reflections | l = 0→29 |
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)] = 0.045 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.97 | w = 1/[σ2(Fo2) + (0.0774P)2 + 2.6466P] where P = (Fo2 + 2Fc2)/3 |
1874 reflections | (Δ/σ)max < 0.001 |
126 parameters | Δρmax = 0.16 e Å−3 |
0 restraints | Δρmin = −0.21 e Å−3 |
C23H28O4 | Z = 8 |
Mr = 368.45 | Mo Kα radiation |
Tetragonal, I41/a | µ = 0.08 mm−1 |
a = 12.7655 (5) Å | T = 100 K |
c = 24.1122 (11) Å | 0.40 × 0.35 × 0.30 mm |
V = 3929.3 (3) Å3 |
Nonius KappaCCD diffractometer | 1437 reflections with I > 2σ(I) |
15112 measured reflections | Rint = 0.066 |
1874 independent reflections |
R[F2 > 2σ(F2)] = 0.045 | 0 restraints |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 0.97 | Δρmax = 0.16 e Å−3 |
1874 reflections | Δρmin = −0.21 e Å−3 |
126 parameters |
Experimental. crystal-to-detector distance 28 mm |
Geometry. 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. |
Refinement. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atom bound to O1 was found on a Fourier-difference map and all the other ones were introduced at calculated positions. All H atoms were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (OH, CH, CH2) or 1.5 (CH3) times that of the parent atom. 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 | ||
O1 | 0.90097 (9) | 0.55453 (10) | 0.11413 (5) | 0.0344 (3) | |
H1 | 0.8849 | 0.4900 | 0.1071 | 0.041* | |
O2 | 0.91448 (10) | 0.36120 (10) | 0.07521 (6) | 0.0381 (4) | |
C1 | 1.05128 (13) | 0.48629 (13) | 0.06526 (7) | 0.0271 (4) | |
C2 | 0.99934 (13) | 0.56736 (13) | 0.09356 (7) | 0.0268 (4) | |
C3 | 1.05006 (13) | 0.66344 (13) | 0.10155 (7) | 0.0253 (4) | |
C4 | 1.15015 (13) | 0.67559 (13) | 0.07997 (7) | 0.0257 (4) | |
H4 | 1.1839 | 0.7393 | 0.0856 | 0.031* | |
C5 | 1.20360 (12) | 0.59754 (12) | 0.05017 (7) | 0.0248 (4) | |
C6 | 1.15240 (13) | 0.50240 (13) | 0.04414 (7) | 0.0275 (4) | |
H6 | 1.1859 | 0.4480 | 0.0256 | 0.033* | |
C7 | 1.00212 (14) | 0.38433 (14) | 0.05800 (8) | 0.0329 (4) | |
H7 | 1.0396 | 0.3332 | 0.0390 | 0.040* | |
C8 | 1.31466 (13) | 0.61727 (13) | 0.02885 (7) | 0.0281 (4) | |
C9 | 1.34553 (15) | 0.53959 (15) | −0.01677 (8) | 0.0399 (5) | |
H9A | 1.3459 | 0.4698 | −0.0019 | 0.060* | |
H9B | 1.4141 | 0.5566 | −0.0304 | 0.060* | |
H9C | 1.2959 | 0.5436 | −0.0466 | 0.060* | |
C10 | 1.39148 (15) | 0.60534 (17) | 0.07746 (8) | 0.0399 (5) | |
H10A | 1.3855 | 0.5362 | 0.0927 | 0.060* | |
H10B | 1.3752 | 0.6561 | 0.1055 | 0.060* | |
H10C | 1.4617 | 0.6163 | 0.0645 | 0.060* | |
C11 | 1.32389 (15) | 0.72815 (15) | 0.00509 (9) | 0.0409 (5) | |
H11A | 1.3943 | 0.7398 | −0.0075 | 0.061* | |
H11B | 1.3068 | 0.7783 | 0.0333 | 0.061* | |
H11C | 1.2764 | 0.7358 | −0.0255 | 0.061* | |
C12 | 1.0000 | 0.7500 | 0.13521 (10) | 0.0276 (5) | |
H12A | 1.0525 | 0.7804 | 0.1587 | 0.033* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0245 (7) | 0.0340 (7) | 0.0447 (8) | −0.0031 (5) | 0.0040 (5) | 0.0010 (6) |
O2 | 0.0338 (7) | 0.0323 (7) | 0.0484 (8) | −0.0079 (5) | −0.0023 (6) | 0.0063 (6) |
C1 | 0.0268 (9) | 0.0241 (9) | 0.0305 (9) | −0.0008 (6) | −0.0032 (7) | 0.0048 (7) |
C2 | 0.0214 (8) | 0.0299 (9) | 0.0290 (8) | 0.0009 (7) | −0.0013 (7) | 0.0043 (7) |
C3 | 0.0245 (8) | 0.0255 (9) | 0.0258 (8) | 0.0033 (6) | −0.0013 (7) | 0.0028 (6) |
C4 | 0.0261 (9) | 0.0224 (8) | 0.0286 (9) | −0.0001 (7) | −0.0025 (7) | 0.0014 (7) |
C5 | 0.0255 (9) | 0.0225 (8) | 0.0263 (8) | 0.0015 (6) | −0.0023 (7) | 0.0028 (7) |
C6 | 0.0279 (9) | 0.0234 (9) | 0.0311 (9) | 0.0027 (7) | −0.0002 (7) | 0.0013 (7) |
C7 | 0.0332 (10) | 0.0263 (9) | 0.0393 (10) | −0.0021 (7) | −0.0025 (8) | 0.0048 (8) |
C8 | 0.0255 (8) | 0.0238 (9) | 0.0349 (9) | 0.0016 (6) | 0.0025 (7) | −0.0003 (7) |
C9 | 0.0324 (10) | 0.0385 (11) | 0.0489 (12) | −0.0014 (8) | 0.0099 (9) | −0.0109 (9) |
C10 | 0.0271 (10) | 0.0490 (12) | 0.0434 (11) | 0.0004 (8) | −0.0025 (8) | 0.0010 (9) |
C11 | 0.0380 (11) | 0.0302 (10) | 0.0545 (12) | 0.0009 (8) | 0.0187 (9) | 0.0087 (9) |
C12 | 0.0251 (12) | 0.0294 (13) | 0.0283 (12) | 0.0016 (9) | 0.000 | 0.000 |
O1—C2 | 1.360 (2) | C8—C9 | 1.533 (2) |
O1—H1 | 0.8660 | C8—C11 | 1.532 (2) |
O2—C7 | 1.229 (2) | C8—C10 | 1.536 (3) |
C1—C6 | 1.403 (2) | C9—H9A | 0.9600 |
C1—C2 | 1.406 (2) | C9—H9B | 0.9600 |
C1—C7 | 1.455 (2) | C9—H9C | 0.9600 |
C2—C3 | 1.400 (2) | C10—H10A | 0.9600 |
C3—C4 | 1.388 (2) | C10—H10B | 0.9600 |
C3—C12 | 1.513 (2) | C10—H10C | 0.9600 |
C4—C5 | 1.405 (2) | C11—H11A | 0.9600 |
C4—H4 | 0.9300 | C11—H11B | 0.9600 |
C5—C6 | 1.387 (2) | C11—H11C | 0.9600 |
C5—C8 | 1.529 (2) | C12—C3i | 1.513 (2) |
C6—H6 | 0.9300 | C12—H12A | 0.9600 |
C7—H7 | 0.9300 | ||
C2—O1—H1 | 105.2 | C5—C8—C10 | 108.61 (15) |
C6—C1—C2 | 120.15 (15) | C9—C8—C10 | 108.63 (15) |
C6—C1—C7 | 118.96 (16) | C11—C8—C10 | 109.15 (16) |
C2—C1—C7 | 120.88 (16) | C8—C9—H9A | 109.5 |
O1—C2—C3 | 118.83 (15) | C8—C9—H9B | 109.5 |
O1—C2—C1 | 121.59 (15) | H9A—C9—H9B | 109.5 |
C3—C2—C1 | 119.57 (15) | C8—C9—H9C | 109.5 |
C4—C3—C2 | 118.15 (15) | H9A—C9—H9C | 109.5 |
C4—C3—C12 | 120.56 (13) | H9B—C9—H9C | 109.5 |
C2—C3—C12 | 121.22 (13) | C8—C10—H10A | 109.5 |
C3—C4—C5 | 124.01 (15) | C8—C10—H10B | 109.5 |
C3—C4—H4 | 118.0 | H10A—C10—H10B | 109.5 |
C5—C4—H4 | 118.0 | C8—C10—H10C | 109.5 |
C6—C5—C4 | 116.47 (15) | H10A—C10—H10C | 109.5 |
C6—C5—C8 | 123.09 (15) | H10B—C10—H10C | 109.5 |
C4—C5—C8 | 120.36 (14) | C8—C11—H11A | 109.5 |
C5—C6—C1 | 121.60 (16) | C8—C11—H11B | 109.5 |
C5—C6—H6 | 119.2 | H11A—C11—H11B | 109.5 |
C1—C6—H6 | 119.2 | C8—C11—H11C | 109.5 |
O2—C7—C1 | 124.52 (17) | H11A—C11—H11C | 109.5 |
O2—C7—H7 | 117.7 | H11B—C11—H11C | 109.5 |
C1—C7—H7 | 117.7 | C3—C12—C3i | 115.1 (2) |
C5—C8—C9 | 111.91 (14) | C3—C12—H12A | 108.5 |
C5—C8—C11 | 110.45 (13) | C3i—C12—H12A | 108.5 |
C9—C8—C11 | 108.03 (15) |
Symmetry code: (i) −x+2, −y+3/2, z. |
C35H48O4 | F(000) = 1160 |
Mr = 532.73 | Dx = 1.189 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 22732 reflections |
a = 12.7635 (10) Å | θ = 3.0–25.7° |
b = 10.0278 (9) Å | µ = 0.08 mm−1 |
c = 23.2629 (13) Å | T = 100 K |
β = 91.496 (5)° | Irregular, colourless |
V = 2976.4 (4) Å3 | 0.18 × 0.15 × 0.09 mm |
Z = 4 |
Nonius KappaCCD diffractometer | 3467 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.063 |
Graphite monochromator | θmax = 25.7°, θmin = 3.0° |
ϕ scans | h = 0→15 |
22732 measured reflections | k = 0→12 |
5621 independent reflections | l = −28→28 |
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)] = 0.056 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0648P)2 + 0.6047P] where P = (Fo2 + 2Fc2)/3 |
5621 reflections | (Δ/σ)max = 0.001 |
358 parameters | Δρmax = 0.22 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C35H48O4 | V = 2976.4 (4) Å3 |
Mr = 532.73 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 12.7635 (10) Å | µ = 0.08 mm−1 |
b = 10.0278 (9) Å | T = 100 K |
c = 23.2629 (13) Å | 0.18 × 0.15 × 0.09 mm |
β = 91.496 (5)° |
Nonius KappaCCD diffractometer | 3467 reflections with I > 2σ(I) |
22732 measured reflections | Rint = 0.063 |
5621 independent reflections |
R[F2 > 2σ(F2)] = 0.056 | 0 restraints |
wR(F2) = 0.147 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.22 e Å−3 |
5621 reflections | Δρmin = −0.24 e Å−3 |
358 parameters |
Experimental. 'crystal-to-detector distance 28 mm' |
Geometry. 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. |
Refinement. Structure solved by direct methods and subsequent Fourier-difference synthesis. All non-hydrogen atoms were refined with anisotropic displacement parameters. The H atoms were introduced at calculated positions and were treated as riding atoms with an isotropic displacement parameter equal to 1.2 (CH, CH2) or 1.5 (CH3) times that of the parent atom. 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 | ||
O1 | 0.16627 (14) | 0.55834 (16) | −0.11191 (7) | 0.0334 (4) | |
O2 | 0.27551 (13) | 0.73692 (15) | −0.08596 (6) | 0.0254 (4) | |
O3 | 0.41987 (13) | 0.92047 (15) | 0.10763 (6) | 0.0271 (4) | |
O4 | 0.54067 (13) | 0.87491 (16) | 0.18227 (6) | 0.0291 (4) | |
C1 | 0.11568 (19) | 0.7044 (2) | −0.03450 (9) | 0.0249 (5) | |
C2 | 0.21211 (18) | 0.7668 (2) | −0.04065 (9) | 0.0225 (5) | |
C3 | 0.24865 (18) | 0.8606 (2) | −0.00088 (9) | 0.0230 (5) | |
C4 | 0.18655 (19) | 0.8897 (2) | 0.04579 (9) | 0.0240 (5) | |
H4 | 0.2110 | 0.9511 | 0.0729 | 0.029* | |
C5 | 0.08878 (19) | 0.8302 (2) | 0.05351 (9) | 0.0245 (5) | |
C6 | 0.05557 (19) | 0.7372 (2) | 0.01237 (9) | 0.0266 (5) | |
H6 | −0.0090 | 0.6957 | 0.0165 | 0.032* | |
C7 | 0.0207 (2) | 0.8616 (2) | 0.10515 (9) | 0.0286 (6) | |
C8 | 0.0209 (3) | 0.7409 (3) | 0.14524 (12) | 0.0624 (10) | |
H8A | −0.0100 | 0.6660 | 0.1255 | 0.094* | |
H8B | −0.0190 | 0.7611 | 0.1786 | 0.094* | |
H8C | 0.0917 | 0.7198 | 0.1569 | 0.094* | |
C9 | −0.0911 (2) | 0.8942 (4) | 0.08515 (13) | 0.0609 (10) | |
H9A | −0.0904 | 0.9694 | 0.0596 | 0.091* | |
H9B | −0.1324 | 0.9151 | 0.1179 | 0.091* | |
H9C | −0.1210 | 0.8187 | 0.0654 | 0.091* | |
C10 | 0.0622 (2) | 0.9799 (3) | 0.13991 (12) | 0.0456 (7) | |
H10A | 0.1315 | 0.9603 | 0.1545 | 0.068* | |
H10B | 0.0169 | 0.9966 | 0.1714 | 0.068* | |
H10C | 0.0643 | 1.0573 | 0.1157 | 0.068* | |
C11 | 0.0809 (2) | 0.6003 (2) | −0.07752 (10) | 0.0325 (6) | |
H11A | 0.0529 | 0.5240 | −0.0574 | 0.039* | |
H11B | 0.0255 | 0.6365 | −0.1022 | 0.039* | |
C12 | 0.22567 (19) | 0.6667 (2) | −0.13319 (9) | 0.0283 (6) | |
C13 | 0.3135 (2) | 0.6069 (2) | −0.16699 (10) | 0.0331 (6) | |
H13A | 0.2840 | 0.5486 | −0.1965 | 0.040* | |
H13B | 0.3576 | 0.5533 | −0.1415 | 0.040* | |
C14 | 0.3805 (2) | 0.7139 (3) | −0.19525 (10) | 0.0341 (6) | |
H14A | 0.4179 | 0.7643 | −0.1656 | 0.041* | |
H14B | 0.4320 | 0.6712 | −0.2191 | 0.041* | |
C15 | 0.3136 (2) | 0.8092 (3) | −0.23222 (10) | 0.0392 (7) | |
H15A | 0.3574 | 0.8797 | −0.2470 | 0.047* | |
H15B | 0.2828 | 0.7611 | −0.2647 | 0.047* | |
C16 | 0.2271 (2) | 0.8698 (3) | −0.19672 (11) | 0.0389 (7) | |
H16A | 0.1831 | 0.9259 | −0.2213 | 0.047* | |
H16B | 0.2583 | 0.9255 | −0.1668 | 0.047* | |
C17 | 0.1594 (2) | 0.7634 (3) | −0.16919 (10) | 0.0324 (6) | |
H17A | 0.1085 | 0.8060 | −0.1450 | 0.039* | |
H17B | 0.1214 | 0.7144 | −0.1990 | 0.039* | |
C18 | 0.35272 (18) | 0.9293 (2) | −0.00902 (9) | 0.0250 (5) | |
H18A | 0.3596 | 0.9494 | −0.0495 | 0.030* | |
H18B | 0.3523 | 1.0134 | 0.0116 | 0.030* | |
C19 | 0.44745 (19) | 0.8499 (2) | 0.01115 (9) | 0.0236 (5) | |
C20 | 0.47819 (18) | 0.8472 (2) | 0.06929 (9) | 0.0242 (5) | |
C21 | 0.56665 (18) | 0.7762 (2) | 0.08793 (9) | 0.0242 (5) | |
C22 | 0.62343 (19) | 0.7048 (2) | 0.04841 (9) | 0.0252 (5) | |
H22 | 0.6814 | 0.6560 | 0.0613 | 0.030* | |
C23 | 0.59633 (19) | 0.7038 (2) | −0.01019 (9) | 0.0243 (5) | |
C24 | 0.50765 (18) | 0.7783 (2) | −0.02726 (9) | 0.0236 (5) | |
H24 | 0.4882 | 0.7798 | −0.0661 | 0.028* | |
C25 | 0.66167 (18) | 0.6231 (2) | −0.05205 (9) | 0.0247 (5) | |
C26 | 0.7762 (2) | 0.6694 (3) | −0.04815 (12) | 0.0468 (7) | |
H26A | 0.7799 | 0.7623 | −0.0578 | 0.070* | |
H26B | 0.8169 | 0.6188 | −0.0745 | 0.070* | |
H26C | 0.8033 | 0.6561 | −0.0097 | 0.070* | |
C27 | 0.6223 (2) | 0.6374 (3) | −0.11444 (9) | 0.0339 (6) | |
H27A | 0.5511 | 0.6070 | −0.1178 | 0.051* | |
H27B | 0.6653 | 0.5849 | −0.1390 | 0.051* | |
H27C | 0.6257 | 0.7294 | −0.1257 | 0.051* | |
C28 | 0.6570 (2) | 0.4756 (2) | −0.03569 (10) | 0.0372 (7) | |
H28A | 0.6819 | 0.4645 | 0.0033 | 0.056* | |
H28B | 0.7003 | 0.4250 | −0.0608 | 0.056* | |
H28C | 0.5860 | 0.4447 | −0.0393 | 0.056* | |
C29 | 0.5994 (2) | 0.7797 (2) | 0.15068 (9) | 0.0297 (6) | |
H29A | 0.5898 | 0.6919 | 0.1672 | 0.036* | |
H29B | 0.6733 | 0.8016 | 0.1541 | 0.036* | |
C30 | 0.43254 (19) | 0.8772 (2) | 0.16626 (9) | 0.0266 (5) | |
C31 | 0.3838 (2) | 0.9826 (2) | 0.20331 (10) | 0.0316 (6) | |
H31A | 0.3128 | 1.0000 | 0.1893 | 0.038* | |
H31B | 0.4234 | 1.0647 | 0.2003 | 0.038* | |
C32 | 0.3814 (2) | 0.9400 (3) | 0.26660 (10) | 0.0374 (6) | |
H32A | 0.4525 | 0.9364 | 0.2823 | 0.045* | |
H32B | 0.3432 | 1.0060 | 0.2882 | 0.045* | |
C33 | 0.3296 (2) | 0.8040 (3) | 0.27383 (10) | 0.0412 (7) | |
H33A | 0.2558 | 0.8105 | 0.2633 | 0.049* | |
H33B | 0.3353 | 0.7772 | 0.3139 | 0.049* | |
C34 | 0.3811 (2) | 0.6987 (3) | 0.23651 (10) | 0.0362 (6) | |
H34A | 0.3440 | 0.6148 | 0.2400 | 0.043* | |
H34B | 0.4530 | 0.6851 | 0.2498 | 0.043* | |
C35 | 0.3794 (2) | 0.7425 (2) | 0.17354 (10) | 0.0310 (6) | |
H35A | 0.4150 | 0.6762 | 0.1508 | 0.037* | |
H35B | 0.3074 | 0.7482 | 0.1594 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0343 (11) | 0.0309 (9) | 0.0354 (9) | −0.0073 (8) | 0.0086 (8) | −0.0078 (7) |
O2 | 0.0250 (9) | 0.0301 (9) | 0.0212 (7) | −0.0013 (7) | 0.0008 (7) | −0.0037 (7) |
O3 | 0.0287 (10) | 0.0291 (9) | 0.0237 (8) | 0.0031 (7) | 0.0010 (7) | −0.0002 (7) |
O4 | 0.0263 (10) | 0.0336 (9) | 0.0271 (8) | 0.0022 (8) | −0.0033 (7) | −0.0042 (7) |
C1 | 0.0280 (14) | 0.0231 (12) | 0.0237 (11) | −0.0008 (10) | 0.0011 (10) | 0.0001 (9) |
C2 | 0.0229 (13) | 0.0224 (12) | 0.0224 (11) | 0.0023 (10) | 0.0032 (9) | 0.0009 (9) |
C3 | 0.0248 (14) | 0.0201 (11) | 0.0240 (11) | 0.0022 (10) | −0.0036 (10) | 0.0016 (9) |
C4 | 0.0276 (14) | 0.0207 (11) | 0.0234 (11) | 0.0023 (10) | −0.0047 (10) | −0.0018 (9) |
C5 | 0.0241 (14) | 0.0243 (12) | 0.0250 (11) | 0.0006 (11) | −0.0006 (10) | 0.0005 (10) |
C6 | 0.0235 (14) | 0.0284 (13) | 0.0280 (12) | −0.0030 (11) | 0.0012 (10) | 0.0010 (10) |
C7 | 0.0285 (15) | 0.0320 (13) | 0.0252 (12) | −0.0001 (11) | 0.0023 (10) | −0.0020 (10) |
C8 | 0.100 (3) | 0.0462 (18) | 0.0427 (17) | 0.0051 (19) | 0.0346 (18) | 0.0069 (14) |
C9 | 0.0315 (18) | 0.099 (3) | 0.0517 (17) | 0.0113 (18) | −0.0005 (14) | −0.0370 (18) |
C10 | 0.0392 (18) | 0.0531 (18) | 0.0452 (16) | −0.0064 (15) | 0.0109 (13) | −0.0180 (14) |
C11 | 0.0299 (15) | 0.0358 (14) | 0.0321 (12) | −0.0064 (12) | 0.0068 (11) | −0.0082 (11) |
C12 | 0.0290 (15) | 0.0302 (13) | 0.0258 (12) | −0.0052 (11) | −0.0005 (10) | −0.0061 (10) |
C13 | 0.0333 (16) | 0.0354 (14) | 0.0308 (13) | 0.0033 (12) | 0.0032 (11) | −0.0085 (11) |
C14 | 0.0292 (15) | 0.0482 (16) | 0.0250 (12) | 0.0061 (12) | 0.0024 (10) | −0.0019 (11) |
C15 | 0.0322 (16) | 0.0588 (18) | 0.0266 (12) | 0.0039 (14) | 0.0016 (11) | 0.0069 (12) |
C16 | 0.0360 (17) | 0.0488 (16) | 0.0319 (13) | 0.0127 (13) | 0.0026 (12) | 0.0104 (12) |
C17 | 0.0261 (14) | 0.0461 (15) | 0.0250 (12) | 0.0016 (12) | 0.0000 (10) | −0.0002 (11) |
C18 | 0.0241 (14) | 0.0243 (12) | 0.0265 (12) | −0.0011 (10) | −0.0006 (10) | 0.0003 (10) |
C19 | 0.0224 (13) | 0.0217 (12) | 0.0266 (11) | −0.0043 (10) | 0.0001 (10) | 0.0013 (10) |
C20 | 0.0242 (14) | 0.0210 (12) | 0.0274 (12) | −0.0016 (10) | 0.0019 (10) | −0.0005 (9) |
C21 | 0.0237 (14) | 0.0243 (12) | 0.0246 (11) | −0.0030 (10) | −0.0009 (10) | 0.0017 (10) |
C22 | 0.0235 (14) | 0.0233 (12) | 0.0288 (12) | 0.0015 (10) | 0.0011 (10) | 0.0013 (10) |
C23 | 0.0234 (13) | 0.0216 (12) | 0.0280 (12) | −0.0047 (10) | 0.0006 (10) | 0.0009 (9) |
C24 | 0.0225 (13) | 0.0247 (12) | 0.0235 (11) | −0.0020 (10) | −0.0002 (10) | −0.0003 (10) |
C25 | 0.0201 (13) | 0.0273 (12) | 0.0270 (12) | −0.0009 (10) | 0.0027 (10) | −0.0004 (10) |
C26 | 0.0294 (16) | 0.0586 (19) | 0.0530 (17) | −0.0065 (14) | 0.0092 (13) | −0.0207 (15) |
C27 | 0.0392 (17) | 0.0357 (14) | 0.0271 (12) | 0.0062 (12) | 0.0053 (11) | 0.0013 (11) |
C28 | 0.0498 (19) | 0.0313 (14) | 0.0305 (13) | 0.0052 (13) | 0.0007 (12) | 0.0008 (11) |
C29 | 0.0302 (15) | 0.0336 (14) | 0.0253 (12) | 0.0036 (11) | −0.0005 (10) | −0.0007 (10) |
C30 | 0.0254 (14) | 0.0316 (13) | 0.0226 (11) | 0.0004 (11) | −0.0019 (10) | 0.0012 (10) |
C31 | 0.0324 (16) | 0.0323 (13) | 0.0301 (13) | 0.0042 (12) | −0.0015 (11) | −0.0056 (11) |
C32 | 0.0371 (17) | 0.0468 (16) | 0.0285 (13) | 0.0059 (13) | 0.0021 (11) | −0.0076 (12) |
C33 | 0.0428 (18) | 0.0532 (17) | 0.0277 (13) | −0.0014 (14) | 0.0055 (12) | 0.0004 (12) |
C34 | 0.0438 (17) | 0.0376 (15) | 0.0272 (12) | −0.0048 (13) | 0.0004 (11) | 0.0024 (11) |
C35 | 0.0337 (16) | 0.0316 (13) | 0.0278 (12) | −0.0014 (11) | 0.0002 (11) | −0.0007 (10) |
O1—C12 | 1.422 (3) | C16—H16B | 0.9700 |
O1—C11 | 1.432 (3) | C17—H17A | 0.9700 |
O2—C2 | 1.379 (3) | C17—H17B | 0.9700 |
O2—C12 | 1.439 (3) | C18—C19 | 1.512 (3) |
O3—C20 | 1.387 (3) | C18—H18A | 0.9700 |
O3—C30 | 1.436 (3) | C18—H18B | 0.9700 |
O4—C30 | 1.420 (3) | C19—C24 | 1.393 (3) |
O4—C29 | 1.430 (3) | C19—C20 | 1.399 (3) |
C1—C6 | 1.389 (3) | C20—C21 | 1.395 (3) |
C1—C2 | 1.392 (3) | C21—C22 | 1.385 (3) |
C1—C11 | 1.505 (3) | C21—C29 | 1.508 (3) |
C2—C3 | 1.391 (3) | C22—C23 | 1.398 (3) |
C3—C4 | 1.392 (3) | C22—H22 | 0.9300 |
C3—C18 | 1.513 (3) | C23—C24 | 1.404 (3) |
C4—C5 | 1.399 (3) | C23—C25 | 1.530 (3) |
C4—H4 | 0.9300 | C24—H24 | 0.9300 |
C5—C6 | 1.395 (3) | C25—C28 | 1.529 (3) |
C5—C7 | 1.534 (3) | C25—C27 | 1.530 (3) |
C6—H6 | 0.9300 | C25—C26 | 1.534 (3) |
C7—C10 | 1.523 (3) | C26—H26A | 0.9600 |
C7—C9 | 1.525 (4) | C26—H26B | 0.9600 |
C7—C8 | 1.528 (4) | C26—H26C | 0.9600 |
C8—H8A | 0.9600 | C27—H27A | 0.9600 |
C8—H8B | 0.9600 | C27—H27B | 0.9600 |
C8—H8C | 0.9600 | C27—H27C | 0.9600 |
C9—H9A | 0.9600 | C28—H28A | 0.9600 |
C9—H9B | 0.9600 | C28—H28B | 0.9600 |
C9—H9C | 0.9600 | C28—H28C | 0.9600 |
C10—H10A | 0.9600 | C29—H29A | 0.9700 |
C10—H10B | 0.9600 | C29—H29B | 0.9700 |
C10—H10C | 0.9600 | C30—C31 | 1.509 (3) |
C11—H11A | 0.9700 | C30—C35 | 1.523 (3) |
C11—H11B | 0.9700 | C31—C32 | 1.534 (3) |
C12—C13 | 1.510 (3) | C31—H31A | 0.9700 |
C12—C17 | 1.523 (3) | C31—H31B | 0.9700 |
C13—C14 | 1.531 (4) | C32—C33 | 1.526 (4) |
C13—H13A | 0.9700 | C32—H32A | 0.9700 |
C13—H13B | 0.9700 | C32—H32B | 0.9700 |
C14—C15 | 1.531 (3) | C33—C34 | 1.526 (4) |
C14—H14A | 0.9700 | C33—H33A | 0.9700 |
C14—H14B | 0.9700 | C33—H33B | 0.9700 |
C15—C16 | 1.522 (4) | C34—C35 | 1.529 (3) |
C15—H15A | 0.9700 | C34—H34A | 0.9700 |
C15—H15B | 0.9700 | C34—H34B | 0.9700 |
C16—C17 | 1.524 (4) | C35—H35A | 0.9700 |
C16—H16A | 0.9700 | C35—H35B | 0.9700 |
C12—O1—C11 | 112.97 (18) | C19—C18—H18A | 108.6 |
C2—O2—C12 | 115.70 (18) | C3—C18—H18A | 108.6 |
C20—O3—C30 | 113.68 (17) | C19—C18—H18B | 108.6 |
C30—O4—C29 | 113.28 (17) | C3—C18—H18B | 108.6 |
C6—C1—C2 | 118.8 (2) | H18A—C18—H18B | 107.6 |
C6—C1—C11 | 121.8 (2) | C24—C19—C20 | 117.7 (2) |
C2—C1—C11 | 119.3 (2) | C24—C19—C18 | 121.50 (19) |
O2—C2—C3 | 117.5 (2) | C20—C19—C18 | 120.8 (2) |
O2—C2—C1 | 121.28 (19) | O3—C20—C21 | 120.96 (19) |
C3—C2—C1 | 121.2 (2) | O3—C20—C19 | 118.0 (2) |
C2—C3—C4 | 118.2 (2) | C21—C20—C19 | 121.0 (2) |
C2—C3—C18 | 120.3 (2) | C22—C21—C20 | 119.4 (2) |
C4—C3—C18 | 121.4 (2) | C22—C21—C29 | 121.2 (2) |
C3—C4—C5 | 122.6 (2) | C20—C21—C29 | 119.4 (2) |
C3—C4—H4 | 118.7 | C21—C22—C23 | 122.1 (2) |
C5—C4—H4 | 118.7 | C21—C22—H22 | 119.0 |
C6—C5—C4 | 117.0 (2) | C23—C22—H22 | 119.0 |
C6—C5—C7 | 120.4 (2) | C22—C23—C24 | 116.7 (2) |
C4—C5—C7 | 122.6 (2) | C22—C23—C25 | 120.0 (2) |
C1—C6—C5 | 122.2 (2) | C24—C23—C25 | 123.36 (19) |
C1—C6—H6 | 118.9 | C19—C24—C23 | 123.1 (2) |
C5—C6—H6 | 118.9 | C19—C24—H24 | 118.4 |
C10—C7—C9 | 107.8 (2) | C23—C24—H24 | 118.4 |
C10—C7—C8 | 107.3 (2) | C28—C25—C27 | 108.25 (19) |
C9—C7—C8 | 110.1 (3) | C28—C25—C23 | 109.16 (19) |
C10—C7—C5 | 112.3 (2) | C27—C25—C23 | 112.50 (19) |
C9—C7—C5 | 110.5 (2) | C28—C25—C26 | 108.7 (2) |
C8—C7—C5 | 108.9 (2) | C27—C25—C26 | 108.5 (2) |
C7—C8—H8A | 109.5 | C23—C25—C26 | 109.65 (19) |
C7—C8—H8B | 109.5 | C25—C26—H26A | 109.5 |
H8A—C8—H8B | 109.5 | C25—C26—H26B | 109.5 |
C7—C8—H8C | 109.5 | H26A—C26—H26B | 109.5 |
H8A—C8—H8C | 109.5 | C25—C26—H26C | 109.5 |
H8B—C8—H8C | 109.5 | H26A—C26—H26C | 109.5 |
C7—C9—H9A | 109.5 | H26B—C26—H26C | 109.5 |
C7—C9—H9B | 109.5 | C25—C27—H27A | 109.5 |
H9A—C9—H9B | 109.5 | C25—C27—H27B | 109.5 |
C7—C9—H9C | 109.5 | H27A—C27—H27B | 109.5 |
H9A—C9—H9C | 109.5 | C25—C27—H27C | 109.5 |
H9B—C9—H9C | 109.5 | H27A—C27—H27C | 109.5 |
C7—C10—H10A | 109.5 | H27B—C27—H27C | 109.5 |
C7—C10—H10B | 109.5 | C25—C28—H28A | 109.5 |
H10A—C10—H10B | 109.5 | C25—C28—H28B | 109.5 |
C7—C10—H10C | 109.5 | H28A—C28—H28B | 109.5 |
H10A—C10—H10C | 109.5 | C25—C28—H28C | 109.5 |
H10B—C10—H10C | 109.5 | H28A—C28—H28C | 109.5 |
O1—C11—C1 | 111.1 (2) | H28B—C28—H28C | 109.5 |
O1—C11—H11A | 109.4 | O4—C29—C21 | 112.14 (19) |
C1—C11—H11A | 109.4 | O4—C29—H29A | 109.2 |
O1—C11—H11B | 109.4 | C21—C29—H29A | 109.2 |
C1—C11—H11B | 109.4 | O4—C29—H29B | 109.2 |
H11A—C11—H11B | 108.0 | C21—C29—H29B | 109.2 |
O1—C12—O2 | 109.71 (17) | H29A—C29—H29B | 107.9 |
O1—C12—C13 | 106.70 (19) | O4—C30—O3 | 109.78 (19) |
O2—C12—C13 | 105.82 (19) | O4—C30—C31 | 105.91 (18) |
O1—C12—C17 | 112.6 (2) | O3—C30—C31 | 107.03 (18) |
O2—C12—C17 | 109.66 (19) | O4—C30—C35 | 112.90 (19) |
C13—C12—C17 | 112.06 (19) | O3—C30—C35 | 109.52 (18) |
C12—C13—C14 | 112.1 (2) | C31—C30—C35 | 111.5 (2) |
C12—C13—H13A | 109.2 | C30—C31—C32 | 111.8 (2) |
C14—C13—H13A | 109.2 | C30—C31—H31A | 109.3 |
C12—C13—H13B | 109.2 | C32—C31—H31A | 109.3 |
C14—C13—H13B | 109.2 | C30—C31—H31B | 109.3 |
H13A—C13—H13B | 107.9 | C32—C31—H31B | 109.3 |
C15—C14—C13 | 111.6 (2) | H31A—C31—H31B | 107.9 |
C15—C14—H14A | 109.3 | C33—C32—C31 | 112.0 (2) |
C13—C14—H14A | 109.3 | C33—C32—H32A | 109.2 |
C15—C14—H14B | 109.3 | C31—C32—H32A | 109.2 |
C13—C14—H14B | 109.3 | C33—C32—H32B | 109.2 |
H14A—C14—H14B | 108.0 | C31—C32—H32B | 109.2 |
C16—C15—C14 | 110.3 (2) | H32A—C32—H32B | 107.9 |
C16—C15—H15A | 109.6 | C32—C33—C34 | 111.2 (2) |
C14—C15—H15A | 109.6 | C32—C33—H33A | 109.4 |
C16—C15—H15B | 109.6 | C34—C33—H33A | 109.4 |
C14—C15—H15B | 109.6 | C32—C33—H33B | 109.4 |
H15A—C15—H15B | 108.1 | C34—C33—H33B | 109.4 |
C15—C16—C17 | 112.1 (2) | H33A—C33—H33B | 108.0 |
C15—C16—H16A | 109.2 | C33—C34—C35 | 110.6 (2) |
C17—C16—H16A | 109.2 | C33—C34—H34A | 109.5 |
C15—C16—H16B | 109.2 | C35—C34—H34A | 109.5 |
C17—C16—H16B | 109.2 | C33—C34—H34B | 109.5 |
H16A—C16—H16B | 107.9 | C35—C34—H34B | 109.5 |
C12—C17—C16 | 111.4 (2) | H34A—C34—H34B | 108.1 |
C12—C17—H17A | 109.4 | C30—C35—C34 | 111.46 (19) |
C16—C17—H17A | 109.4 | C30—C35—H35A | 109.3 |
C12—C17—H17B | 109.4 | C34—C35—H35A | 109.3 |
C16—C17—H17B | 109.4 | C30—C35—H35B | 109.3 |
H17A—C17—H17B | 108.0 | C34—C35—H35B | 109.3 |
C19—C18—C3 | 114.76 (18) | H35A—C35—H35B | 108.0 |
Experimental details
(I) | (II) | |
Crystal data | ||
Chemical formula | C23H28O4 | C35H48O4 |
Mr | 368.45 | 532.73 |
Crystal system, space group | Tetragonal, I41/a | Monoclinic, P21/n |
Temperature (K) | 100 | 100 |
a, b, c (Å) | 12.7655 (5), 12.7655 (5), 24.1122 (11) | 12.7635 (10), 10.0278 (9), 23.2629 (13) |
α, β, γ (°) | 90, 90, 90 | 90, 91.496 (5), 90 |
V (Å3) | 3929.3 (3) | 2976.4 (4) |
Z | 8 | 4 |
Radiation type | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.08 |
Crystal size (mm) | 0.40 × 0.35 × 0.30 | 0.18 × 0.15 × 0.09 |
Data collection | ||
Diffractometer | Nonius KappaCCD diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | – | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15112, 1874, 1437 | 22732, 5621, 3467 |
Rint | 0.066 | 0.063 |
(sin θ/λ)max (Å−1) | 0.609 | 0.610 |
Refinement | ||
R[F2 > 2σ(F2)], wR(F2), S | 0.045, 0.130, 0.97 | 0.056, 0.147, 1.02 |
No. of reflections | 1874 | 5621 |
No. of parameters | 126 | 358 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.16, −0.21 | 0.22, −0.24 |
Computer programs: KappaCCD Server Software (Nonius, 1998), DENZO–SMN (Otwinowski & Minor, 1997), DENZO–SMN, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL and PLATON (Spek, 2000).
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.87 | 1.85 | 2.6461 (18) | 151 |
In the course of our studies on homooxacalixarenes and related compounds, we obtained single crystals of two species containing two equivalent p-tert-butyl-o-methylene linked phenol or phenol-derived subunits, ortho formyl groups being also present in compound (I) and spiro systems involving 1,3-benzodioxin and cyclohexane being featured in compound (II), which is the diacetal compound obtained by condensation of a bis(hydroxymethyl)diphenol with cyclohexanone.
The asymmetric unit in (I) contains half a molecule, with methylene atom C12 located on a binary axis. The two aromatic rings define a dihedral angle of 61.68 (4)°, similar to that in 2,2'-methylenebisphenol [61.81 (8)°] and somewhat lower than the values generally observed in uncomplexed diphenols in `butterfly' conformation (Thuéry et al., 2000, and references therein) [C2—C3—C12—C3i = 101.23 (16)°; symmetry code: (i) 2 − x, 1.5–y, z]. However, in contrast to the previously reported diphenol, the phenol O atoms in (I) are in distal positions; this conformation can be ascribed to the absence of a hydrogen bond between the two phenol O atoms, as is frequently observed in diphenols. The two intramolecular hydrogen bonds in (I) involve the phenol and aldehyde groups in each half-molecule. Atoms O2 and H1 are displaced only 0.053 (3) and 0.022 (3) Å from the plane of the aromatic ring. The latter and the O1—H1···O2—C7—C1—C2 six-membered ring are thus nearly coplanar. The packing does not involve intermolecular hydrogen bonds, or π–π or CH–π interactions, in contrast to the situation that is frequently observed in such compounds (Masci et al., 2002), but instead is effected by normal van der Waals forces.
Compound (II) possesses a pseudo-binary axis only, as does the related compound 2,2,2',2',6,6'-hexamethyl-8,8'-methylenebis(4H-1,3-benzodioxin), (III) (Masci et al., 2002). Each half-molecule contains a cyclic acetal group in the form of a heterocyclic 1,3-dioxin ring, which is fused to an aromatic ring, giving the 1,3-benzodioxin moiety. Compound (II) differs from (III)? by replacement of the 6-methyl group by 6-tert-butyl substituents and of the 2,2-dimethyl substituents by the pentamethylene unit, giving rise to the spiro system. A `butterfly' conformation, with the dioxin rings in distal positions, is observed in both (I) and (II)?. The dihedral angle between the two aromatic rings in (II) is 65.67 (6)°, slightly larger than that in (I) and smaller than that in (III) [72.17 (8)°]. The C2—C3—C18—C19 and C3—C18—C19—C20 torsion angles in (II) are 82.0 (3) and 81.2 (3)°, respectively, close to the values in (III)? and in 6,6',7,7'-tetrachloro-8,8'-methylenebis(4H-1,3-benzodioxin) (88.2°; Ferguson et al., 1989). As in the previous benzodioxin derivatives, the 1,3-dioxin rings in (II) are in distorted half-chair conformations. In the first ring, atoms O1 and C12 are −0.340 (4) and 0.373 (4) Å from the mean plane defined by atoms O2, C1, C2 and C11 (r.m.s. deviation 0.004 Å) and, in the second ring, atoms O4 and C30 are at 0.201 (4) and −0.505 (4) Å from the mean plane defined by atoms O3, C20, C21 and C29 (r.m.s. deviation 0.0008 Å). It has been noted previously that the single C—O bonds in such compounds are not of equal length, the bonds analogous to O1—C12 in (II) being shorter by about 0.03–0.05 Å than those analogous to O1—C11 (and possibly also O2—C12) (Hamada et al., 1987; Ferguson et al., 1989; Irving & Irving, 1989a,b). The same trend seems to apply to the 1,3-benzodioxin compounds we reported recently (Masci et al., 2002) and to (II), in spite of the different substituents present, with an overall mean value of 1.415 (9) Å for the O1—C12 bond and its counterparts, and 1.436 (8) Å for the O1—C11 and O2—C12 bonds and their counterparts [for (II), O1—C12 = 1.422 (3) Å, O1—C11 = 1.432 (3) Å, O2—C12 = 1.439 (3) Å, O4—C30 = 1.420 (3) Å, O4—C29 = 1.430 (3) Å and O3–C30 1.436 (3) Å]. The C12—C17 and C30–C35 rings are both in chair conformations, although with a difference in their linking to the 1,3-dioxin ring; the C12–C17 ring is bound in such a way that the alcohol-derived atom O1 is in an equatorial position, whereas the C30–C35 ring has phenol-derived atom O3 in an equatorial position. This difference is not surprising, since there is no size difference between these two groups and hence no increase in stability is expected upon location of one or the other in an equatorial position. No significant π–π interaction is present in the packing and only two very weak CH–π interactions may be noted, both of them involving tert-butyl H atoms [H9A···Cg1i = 2.88 Å and C9–H9A···Cg1i = 163°, and H28C···Cg2ii = 2.73 Å and C28–H28C···Cg2ii 143°; Cg1 and Cg2 are the centroids of the C1–C6 and C19–C24 rings; symmetry codes: (i) −x, 2 − y, –z; (ii) 1 − x, 1 − y, −z]. The latter interaction corresponds to the formation of loosely associated dimers, with the tert-butyl group containing atom C28 in each molecule included in the `cup' formed by the other ?tert-butyl group?.