Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801020281/tk6043sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801020281/tk6043Isup2.hkl |
CCDC reference: 180531
Key indicators
- Single-crystal X-ray study
- T = 170 K
- Mean (C-C) = 0.004 Å
- H-atom completeness 100%
- R factor = 0.047
- wR factor = 0.139
- Data-to-parameter ratio = 14.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
ABSMU_01 Alert C The ratio of given/expected absorption coefficient lies outside the range 0.99 <> 1.01 Calculated value of mu = 0.072 Value of mu given = 0.073 PLAT_030 Alert C Refined Extinction parameter within range .... 3.00 Sigma General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C32 H36 O2 Atom count from the _atom_site data: C32 H35.88600 O2.114 CELLZ_01 From the CIF: _cell_formula_units_Z 4 From the CIF: _chemical_formula_sum C32 H36 O2 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 128.00 128.00 0.00 H 144.00 143.54 0.46 O 8.00 8.46 -0.46 Difference between formula and atom_site contents detected. WARNING: H atoms missing from atom site list. Is this intentional?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
2 Alert Level C = Please check
Crystals suitable for structural determination were grown by slow evaporation from a deutero-chloroform solution of the compound.
Hydrogen atoms were added at idealized positions, constrained to ride on the atom to which they were bonded and given displacement parameters equal to 1.2 or 1.5 times Uiso of that bonded atom. Residual electron density (> 0.5 e- per Å3) was discovered in later difference maps, located approximately 1.4 Å from C7'and 0.4 Å from H7'A. As the distance was nearly an ideal alcoholic C–O bond length, the residual density was assigned to an oxygen atom, O3B. The neighboring proton (H7'A) and O3B were modeled as two parts of a disordered group, with the relative occupancies of the two parts allowed to refine. The final occupancies of the two parts were 88.566 (7)% for the proton and 11.434 (7)% for O3B. No protons were modeled for O3B. The resultant difference map was greatly improved.
Data collection: SMART (Bruker, 1997a); cell refinement: SMART; data reduction: SAINT (Bruker, 1997a); program(s) used to solve structure: SHELXTL (Bruker, 1997b); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Fig. 1. Displacement ellipsoid plot rendered with 50% probability ellipsoids (Bruker, 1997). |
C32H36O2 | F(000) = 976 |
Mr = 452.61 | Dx = 1.193 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 12.2381 (9) Å | Cell parameters from 4886 reflections |
b = 21.8866 (15) Å | θ = 2.4–22.4° |
c = 10.3089 (7) Å | µ = 0.07 mm−1 |
β = 113.690 (1)° | T = 170 K |
V = 2528.6 (3) Å3 | Block, colorless |
Z = 4 | 0.3 × 0.15 × 0.1 mm |
CCD area-detector diffractometer | 2142 reflections with I > \2s(I) |
Radiation source: fine-focus sealed tube | Rint = 0.099 |
Graphite monochromator | θmax = 25.1°, θmin = 1.8° |
ψ and ω scans | h = −14→14 |
23714 measured reflections | k = −26→26 |
4484 independent reflections | l = −12→12 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.139 | w = 1/[σ2(Fo2) + (0.0575P)2] where P = (Fo2 + 2Fc2)/3 |
S = 0.94 | (Δ/σ)max < 0.001 |
4484 reflections | Δρmax = 0.25 e Å−3 |
313 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0024 (8) |
C32H36O2 | V = 2528.6 (3) Å3 |
Mr = 452.61 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 12.2381 (9) Å | µ = 0.07 mm−1 |
b = 21.8866 (15) Å | T = 170 K |
c = 10.3089 (7) Å | 0.3 × 0.15 × 0.1 mm |
β = 113.690 (1)° |
CCD area-detector diffractometer | 2142 reflections with I > \2s(I) |
23714 measured reflections | Rint = 0.099 |
4484 independent reflections |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.139 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.94 | Δρmax = 0.25 e Å−3 |
4484 reflections | Δρmin = −0.21 e Å−3 |
313 parameters |
Experimental. NMR shifts (δ) and coupling constants (J, in Hz) of (Ia) in CDCl3 at 600 MHz # 13 C 1H # 13 C 1H 1 200.3 - 1' 198.0 - 2 126.0 5.68 2' 131.7 - 3 164.2 - 3' 155.8 - 4 46.7 1.42,1.89 4' 46.0 2.40,2.50 5 33.0 - 5' 33.5 - 6 51.0 2.04,2.11 6' 52.1 2.32,2.36 7 55.3 2.71 7' 33.2 2.54,2.78 8 43.9 4.17 8' 36.2 3.37 9 145.0 - 9' 141.8 - 10 128.2 7.20 10' 128.0 6.98 11 128.7 7.31 11' 128.6 7.22 12 126.7 7.22 12' 127.0 7.17 15 28.0 0.71 15' 27.9 1.12 16 28.5 0.86 16' 29.5 1.16 J4,4 = 18.5 J4',4' = 18.0 J6,6 = 16.0 J6',6' = 15.5 J7,8 = 0 J7',7' = 19.5 J7,8' = 3.5 J7',8' = 5.0,12.0 A parameter describing extinction was included and refined to a final value of x = 0.0024 (8). |
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. 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 | Occ. (<1) | |
O1 | 0.36245 (17) | 0.74468 (9) | 0.8237 (2) | 0.0321 (5) | |
C9' | 0.3943 (2) | 1.03903 (12) | 0.7511 (3) | 0.0228 (7) | |
C3' | 0.2773 (2) | 0.89476 (12) | 0.8749 (3) | 0.0222 (7) | |
C4' | 0.2047 (2) | 0.88207 (12) | 0.9595 (3) | 0.0255 (7) | |
H4'A | 0.1368 | 0.9110 | 0.9294 | 0.031* | |
H4'B | 0.2548 | 0.8902 | 1.0606 | 0.031* | |
C5' | 0.1556 (2) | 0.81676 (12) | 0.9458 (3) | 0.0255 (7) | |
C11' | 0.5107 (3) | 1.11842 (13) | 0.7029 (3) | 0.0335 (8) | |
H11' | 0.5833 | 1.1313 | 0.6986 | 0.040* | |
C2' | 0.3297 (2) | 0.85019 (12) | 0.8292 (3) | 0.0221 (7) | |
C7' | 0.2868 (3) | 0.96076 (12) | 0.8406 (3) | 0.0260 (7) | |
H7'A | 0.3015 | 0.9857 | 0.9261 | 0.031* | 0.886 (7) |
H7'B | 0.2099 | 0.9740 | 0.7661 | 0.031* | |
O3 | 0.2961 (16) | 0.9985 (8) | 0.9559 (19) | 0.045 (9)* | 0.114 (7) |
C14' | 0.3014 (3) | 1.08048 (12) | 0.7167 (3) | 0.0279 (7) | |
H14' | 0.2287 | 1.0681 | 0.7214 | 0.034* | |
C16' | 0.1088 (3) | 0.80508 (13) | 1.0600 (3) | 0.0344 (8) | |
H116 | 0.0778 | 0.7633 | 1.0508 | 0.052* | |
H216 | 0.0448 | 0.8341 | 1.0490 | 0.052* | |
H316 | 0.1738 | 0.8103 | 1.1536 | 0.052* | |
C8' | 0.3856 (2) | 0.97276 (12) | 0.7902 (3) | 0.0232 (7) | |
H8' | 0.4624 | 0.9630 | 0.8717 | 0.028* | |
C1' | 0.3195 (2) | 0.78592 (13) | 0.8677 (3) | 0.0243 (7) | |
C12' | 0.4166 (3) | 1.15853 (13) | 0.6680 (3) | 0.0324 (8) | |
H12' | 0.4235 | 1.1990 | 0.6388 | 0.039* | |
C13' | 0.3126 (3) | 1.13940 (13) | 0.6759 (3) | 0.0326 (8) | |
H13' | 0.2476 | 1.1670 | 0.6530 | 0.039* | |
C6' | 0.2590 (2) | 0.77349 (12) | 0.9658 (3) | 0.0287 (7) | |
H6'A | 0.3187 | 0.7768 | 1.0647 | 0.034* | |
H6'B | 0.2286 | 0.7310 | 0.9508 | 0.034* | |
C15' | 0.0536 (3) | 0.80706 (13) | 0.8006 (3) | 0.0329 (8) | |
H115 | 0.0240 | 0.7651 | 0.7937 | 0.049* | |
H215 | 0.0827 | 0.8143 | 0.7261 | 0.049* | |
H315 | −0.0113 | 0.8357 | 0.7890 | 0.049* | |
C10' | 0.5000 (3) | 1.05912 (13) | 0.7445 (3) | 0.0302 (7) | |
H10' | 0.5657 | 1.0319 | 0.7689 | 0.036* | |
C5 | 0.1482 (3) | 1.00026 (13) | 0.3157 (3) | 0.0312 (8) | |
C10 | 0.5730 (3) | 0.82195 (13) | 0.7023 (3) | 0.0306 (8) | |
H10A | 0.5250 | 0.8195 | 0.6036 | 0.037* | |
C11 | 0.6916 (3) | 0.80428 (13) | 0.7532 (4) | 0.0388 (8) | |
H11A | 0.7244 | 0.7896 | 0.6897 | 0.047* | |
C15 | 0.1685 (3) | 1.03352 (15) | 0.1968 (3) | 0.0446 (9) | |
H15A | 0.0915 | 1.0466 | 0.1245 | 0.067* | |
H15B | 0.2078 | 1.0059 | 0.1541 | 0.067* | |
H15C | 0.2191 | 1.0694 | 0.2356 | 0.067* | |
C6 | 0.0726 (3) | 0.94340 (13) | 0.2578 (3) | 0.0347 (8) | |
H6A | −0.0083 | 0.9562 | 0.1919 | 0.042* | |
H6B | 0.1080 | 0.9195 | 0.2028 | 0.042* | |
C12 | 0.7617 (3) | 0.80811 (14) | 0.8955 (4) | 0.0406 (9) | |
H12A | 0.8428 | 0.7956 | 0.9307 | 0.049* | |
C16 | 0.0861 (3) | 1.04352 (13) | 0.3814 (3) | 0.0395 (9) | |
H16A | 0.0714 | 1.0221 | 0.4563 | 0.059* | |
H16B | 0.0100 | 1.0571 | 0.3082 | 0.059* | |
H16C | 0.1372 | 1.0791 | 0.4218 | 0.059* | |
C13 | 0.7150 (3) | 0.82991 (14) | 0.9869 (4) | 0.0390 (9) | |
H13A | 0.7642 | 0.8330 | 1.0851 | 0.047* | |
C1 | 0.0618 (3) | 0.90298 (14) | 0.3694 (3) | 0.0327 (8) | |
C2 | 0.1644 (2) | 0.90066 (13) | 0.5062 (3) | 0.0284 (7) | |
H2A | 0.1613 | 0.8738 | 0.5771 | 0.034* | |
C7 | 0.3747 (2) | 0.92708 (12) | 0.6696 (3) | 0.0227 (7) | |
H7A | 0.4435 | 0.9354 | 0.6434 | 0.027* | |
C9 | 0.5233 (2) | 0.84313 (12) | 0.7937 (3) | 0.0239 (7) | |
C8 | 0.3922 (2) | 0.86107 (11) | 0.7313 (3) | 0.0208 (7) | |
H8A | 0.3524 | 0.8334 | 0.6484 | 0.025* | |
C14 | 0.5957 (3) | 0.84752 (13) | 0.9367 (3) | 0.0308 (8) | |
H14A | 0.5639 | 0.8626 | 1.0007 | 0.037* | |
C3 | 0.2624 (2) | 0.93474 (12) | 0.5356 (3) | 0.0228 (7) | |
C4 | 0.2692 (2) | 0.97973 (13) | 0.4287 (3) | 0.0278 (7) | |
H4A | 0.3164 | 0.9612 | 0.3803 | 0.033* | |
H4B | 0.3129 | 1.0164 | 0.4799 | 0.033* | |
O0 | −0.02593 (19) | 0.87050 (10) | 0.3461 (2) | 0.0470 (6) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0348 (13) | 0.0235 (12) | 0.0395 (13) | 0.0032 (10) | 0.0166 (11) | −0.0008 (10) |
C9' | 0.0243 (17) | 0.0183 (16) | 0.0221 (16) | −0.0038 (13) | 0.0053 (13) | −0.0033 (13) |
C3' | 0.0208 (16) | 0.0221 (16) | 0.0202 (16) | −0.0003 (13) | 0.0047 (13) | 0.0002 (13) |
C4' | 0.0290 (17) | 0.0205 (17) | 0.0259 (17) | 0.0018 (13) | 0.0100 (14) | 0.0001 (13) |
C5' | 0.0270 (17) | 0.0201 (16) | 0.0293 (18) | 0.0024 (13) | 0.0111 (15) | 0.0033 (13) |
C11' | 0.0305 (19) | 0.0321 (19) | 0.038 (2) | −0.0044 (15) | 0.0142 (16) | 0.0052 (16) |
C2' | 0.0225 (16) | 0.0216 (16) | 0.0194 (16) | −0.0024 (13) | 0.0056 (13) | 0.0001 (13) |
C7' | 0.0334 (18) | 0.0190 (16) | 0.0256 (17) | −0.0017 (13) | 0.0117 (14) | −0.0021 (13) |
C14' | 0.0296 (18) | 0.0219 (17) | 0.0312 (18) | −0.0015 (14) | 0.0110 (15) | −0.0037 (14) |
C16' | 0.0373 (19) | 0.0293 (18) | 0.041 (2) | 0.0029 (15) | 0.0202 (17) | 0.0032 (15) |
C8' | 0.0218 (16) | 0.0204 (16) | 0.0257 (17) | 0.0010 (13) | 0.0077 (14) | −0.0013 (13) |
C1' | 0.0215 (16) | 0.0209 (17) | 0.0246 (18) | 0.0027 (13) | 0.0030 (14) | −0.0013 (13) |
C12' | 0.039 (2) | 0.0209 (17) | 0.0354 (19) | −0.0047 (15) | 0.0127 (16) | 0.0011 (14) |
C13' | 0.0320 (19) | 0.0234 (18) | 0.042 (2) | 0.0017 (14) | 0.0140 (16) | −0.0032 (15) |
C6' | 0.0298 (18) | 0.0221 (17) | 0.0344 (19) | 0.0013 (14) | 0.0131 (15) | 0.0034 (14) |
C15' | 0.0340 (19) | 0.0279 (18) | 0.0353 (19) | 0.0000 (14) | 0.0123 (16) | 0.0003 (15) |
C10' | 0.0262 (18) | 0.0273 (18) | 0.0356 (19) | −0.0009 (14) | 0.0107 (15) | 0.0029 (15) |
C5 | 0.0352 (19) | 0.0284 (17) | 0.0242 (18) | 0.0029 (15) | 0.0058 (15) | 0.0017 (14) |
C10 | 0.0301 (19) | 0.0290 (18) | 0.0355 (19) | 0.0046 (15) | 0.0160 (16) | −0.0004 (15) |
C11 | 0.036 (2) | 0.033 (2) | 0.055 (2) | 0.0050 (16) | 0.0262 (19) | 0.0036 (17) |
C15 | 0.052 (2) | 0.041 (2) | 0.034 (2) | 0.0020 (17) | 0.0108 (17) | 0.0108 (17) |
C6 | 0.0350 (19) | 0.037 (2) | 0.0252 (18) | 0.0028 (15) | 0.0045 (15) | 0.0011 (15) |
C12 | 0.0264 (19) | 0.033 (2) | 0.061 (3) | 0.0031 (15) | 0.0154 (19) | 0.0065 (18) |
C16 | 0.040 (2) | 0.0335 (19) | 0.037 (2) | 0.0122 (16) | 0.0071 (16) | 0.0037 (16) |
C13 | 0.032 (2) | 0.039 (2) | 0.037 (2) | 0.0006 (16) | 0.0055 (17) | 0.0035 (16) |
C1 | 0.0290 (19) | 0.0297 (18) | 0.035 (2) | 0.0009 (15) | 0.0077 (16) | −0.0038 (15) |
C2 | 0.0282 (18) | 0.0258 (17) | 0.0276 (18) | 0.0030 (14) | 0.0074 (15) | 0.0053 (14) |
C7 | 0.0233 (16) | 0.0190 (15) | 0.0252 (17) | 0.0012 (13) | 0.0090 (14) | 0.0019 (13) |
C9 | 0.0268 (17) | 0.0165 (15) | 0.0285 (18) | 0.0026 (13) | 0.0111 (15) | 0.0030 (13) |
C8 | 0.0246 (16) | 0.0162 (15) | 0.0212 (16) | 0.0013 (12) | 0.0086 (14) | 0.0000 (12) |
C14 | 0.0285 (18) | 0.0331 (19) | 0.0288 (18) | 0.0002 (15) | 0.0092 (15) | −0.0008 (15) |
C3 | 0.0249 (17) | 0.0197 (16) | 0.0229 (16) | 0.0046 (13) | 0.0088 (14) | −0.0016 (13) |
C4 | 0.0366 (19) | 0.0250 (17) | 0.0243 (17) | 0.0024 (14) | 0.0151 (15) | 0.0034 (13) |
O0 | 0.0306 (13) | 0.0506 (15) | 0.0501 (15) | −0.0087 (12) | 0.0059 (12) | −0.0009 (12) |
O1—C1' | 1.220 (3) | C10'—H10' | 0.9500 |
C9'—C14' | 1.384 (4) | C5—C6 | 1.522 (4) |
C9'—C10' | 1.393 (4) | C5—C15 | 1.530 (4) |
C9'—C8' | 1.520 (4) | C5—C16 | 1.531 (4) |
C3'—C2' | 1.351 (4) | C5—C4 | 1.538 (4) |
C3'—C4' | 1.500 (4) | C10—C11 | 1.386 (4) |
C3'—C7' | 1.503 (4) | C10—C9 | 1.390 (4) |
C4'—C5' | 1.535 (3) | C10—H10A | 0.9500 |
C4'—H4'A | 0.9900 | C11—C12 | 1.373 (4) |
C4'—H4'B | 0.9900 | C11—H11A | 0.9500 |
C5'—C16' | 1.524 (4) | C15—H15A | 0.9800 |
C5'—C6' | 1.527 (4) | C15—H15B | 0.9800 |
C5'—C15' | 1.531 (4) | C15—H15C | 0.9800 |
C11'—C12' | 1.377 (4) | C6—C1 | 1.499 (4) |
C11'—C10' | 1.390 (4) | C6—H6A | 0.9900 |
C11'—H11' | 0.9500 | C6—H6B | 0.9900 |
C2'—C1' | 1.480 (4) | C12—C13 | 1.370 (4) |
C2'—C8 | 1.510 (3) | C12—H12A | 0.9500 |
C7'—O3 | 1.414 (18) | C16—H16A | 0.9800 |
C7'—C8' | 1.518 (4) | C16—H16B | 0.9800 |
C7'—H7'A | 0.9900 | C16—H16C | 0.9800 |
C7'—H7'B | 0.9900 | C13—C14 | 1.392 (4) |
C14'—C13' | 1.380 (4) | C13—H13A | 0.9500 |
C14'—H14' | 0.9500 | C1—O0 | 1.228 (3) |
C16'—H116 | 0.9800 | C1—C2 | 1.464 (4) |
C16'—H216 | 0.9800 | C2—C3 | 1.340 (4) |
C16'—H316 | 0.9800 | C2—H2A | 0.9500 |
C8'—C7 | 1.558 (4) | C7—C3 | 1.516 (4) |
C8'—H8' | 1.0000 | C7—C8 | 1.558 (3) |
C1'—C6' | 1.498 (4) | C7—H7A | 1.0000 |
C12'—C13' | 1.373 (4) | C9—C14 | 1.385 (4) |
C12'—H12' | 0.9500 | C9—C8 | 1.522 (4) |
C13'—H13' | 0.9500 | C8—H8A | 1.0000 |
C6'—H6'A | 0.9900 | C14—H14A | 0.9500 |
C6'—H6'B | 0.9900 | C3—C4 | 1.505 (4) |
C15'—H115 | 0.9800 | C4—H4A | 0.9900 |
C15'—H215 | 0.9800 | C4—H4B | 0.9900 |
C15'—H315 | 0.9800 | ||
C14'—C9'—C10' | 117.6 (3) | C11'—C10'—H10' | 119.5 |
C14'—C9'—C8' | 123.8 (2) | C9'—C10'—H10' | 119.5 |
C10'—C9'—C8' | 118.6 (2) | C6—C5—C15 | 110.1 (2) |
C2'—C3'—C4' | 122.9 (2) | C6—C5—C16 | 110.4 (3) |
C2'—C3'—C7' | 121.3 (3) | C15—C5—C16 | 109.2 (2) |
C4'—C3'—C7' | 115.8 (2) | C6—C5—C4 | 107.9 (2) |
C3'—C4'—C5' | 114.8 (2) | C15—C5—C4 | 109.2 (2) |
C3'—C4'—H4'A | 108.6 | C16—C5—C4 | 110.1 (2) |
C5'—C4'—H4'A | 108.6 | C11—C10—C9 | 120.9 (3) |
C3'—C4'—H4'B | 108.6 | C11—C10—H10A | 119.5 |
C5'—C4'—H4'B | 108.6 | C9—C10—H10A | 119.5 |
H4'A—C4'—H4'B | 107.5 | C12—C11—C10 | 119.8 (3) |
C16'—C5'—C6' | 109.9 (2) | C12—C11—H11A | 120.1 |
C16'—C5'—C15' | 108.7 (2) | C10—C11—H11A | 120.1 |
C6'—C5'—C15' | 110.6 (2) | C5—C15—H15A | 109.5 |
C16'—C5'—C4' | 109.9 (2) | C5—C15—H15B | 109.5 |
C6'—C5'—C4' | 107.0 (2) | H15A—C15—H15B | 109.5 |
C15'—C5'—C4' | 110.8 (2) | C5—C15—H15C | 109.5 |
C12'—C11'—C10' | 120.2 (3) | H15A—C15—H15C | 109.5 |
C12'—C11'—H11' | 119.9 | H15B—C15—H15C | 109.5 |
C10'—C11'—H11' | 119.9 | C1—C6—C5 | 114.1 (2) |
C3'—C2'—C1' | 119.4 (2) | C1—C6—H6A | 108.7 |
C3'—C2'—C8 | 123.9 (2) | C5—C6—H6A | 108.7 |
C1'—C2'—C8 | 116.6 (2) | C1—C6—H6B | 108.7 |
O3—C7'—C3' | 110.5 (8) | C5—C6—H6B | 108.7 |
O3—C7'—C8' | 112.4 (8) | H6A—C6—H6B | 107.6 |
C3'—C7'—C8' | 113.3 (2) | C13—C12—C11 | 120.2 (3) |
O3—C7'—H7'A | 5.7 | C13—C12—H12A | 119.9 |
C3'—C7'—H7'A | 108.9 | C11—C12—H12A | 119.9 |
C8'—C7'—H7'A | 108.9 | C5—C16—H16A | 109.5 |
O3—C7'—H7'B | 102.2 | C5—C16—H16B | 109.5 |
C3'—C7'—H7'B | 108.9 | H16A—C16—H16B | 109.5 |
C8'—C7'—H7'B | 108.9 | C5—C16—H16C | 109.5 |
H7'A—C7'—H7'B | 107.7 | H16A—C16—H16C | 109.5 |
C13'—C14'—C9' | 121.2 (3) | H16B—C16—H16C | 109.5 |
C13'—C14'—H14' | 119.4 | C12—C13—C14 | 120.4 (3) |
C9'—C14'—H14' | 119.4 | C12—C13—H13A | 119.8 |
C5'—C16'—H116 | 109.5 | C14—C13—H13A | 119.8 |
C5'—C16'—H216 | 109.5 | O0—C1—C2 | 120.8 (3) |
H116—C16'—H216 | 109.5 | O0—C1—C6 | 122.1 (3) |
C5'—C16'—H316 | 109.5 | C2—C1—C6 | 117.0 (3) |
H116—C16'—H316 | 109.5 | C3—C2—C1 | 122.8 (3) |
H216—C16'—H316 | 109.5 | C3—C2—H2A | 118.6 |
C7'—C8'—C9' | 113.9 (2) | C1—C2—H2A | 118.6 |
C7'—C8'—C7 | 109.7 (2) | C3—C7—C8' | 114.3 (2) |
C9'—C8'—C7 | 113.2 (2) | C3—C7—C8 | 113.6 (2) |
C7'—C8'—H8' | 106.5 | C8'—C7—C8 | 108.4 (2) |
C9'—C8'—H8' | 106.5 | C3—C7—H7A | 106.7 |
C7—C8'—H8' | 106.5 | C8'—C7—H7A | 106.7 |
O1—C1'—C2' | 120.6 (3) | C8—C7—H7A | 106.7 |
O1—C1'—C6' | 121.3 (2) | C14—C9—C10 | 118.5 (3) |
C2'—C1'—C6' | 118.1 (2) | C14—C9—C8 | 123.1 (3) |
C13'—C12'—C11' | 119.2 (3) | C10—C9—C8 | 118.3 (2) |
C13'—C12'—H12' | 120.4 | C2'—C8—C9 | 114.1 (2) |
C11'—C12'—H12' | 120.4 | C2'—C8—C7 | 113.3 (2) |
C12'—C13'—C14' | 120.7 (3) | C9—C8—C7 | 111.1 (2) |
C12'—C13'—H13' | 119.6 | C2'—C8—H8A | 105.8 |
C14'—C13'—H13' | 119.6 | C9—C8—H8A | 105.8 |
C1'—C6'—C5' | 113.8 (2) | C7—C8—H8A | 105.8 |
C1'—C6'—H6'A | 108.8 | C9—C14—C13 | 120.2 (3) |
C5'—C6'—H6'A | 108.8 | C9—C14—H14A | 119.9 |
C1'—C6'—H6'B | 108.8 | C13—C14—H14A | 119.9 |
C5'—C6'—H6'B | 108.8 | C2—C3—C4 | 120.4 (3) |
H6'A—C6'—H6'B | 107.7 | C2—C3—C7 | 123.1 (3) |
C5'—C15'—H115 | 109.5 | C4—C3—C7 | 116.3 (2) |
C5'—C15'—H215 | 109.5 | C3—C4—C5 | 115.2 (2) |
H115—C15'—H215 | 109.5 | C3—C4—H4A | 108.5 |
C5'—C15'—H315 | 109.5 | C5—C4—H4A | 108.5 |
H115—C15'—H315 | 109.5 | C3—C4—H4B | 108.5 |
H215—C15'—H315 | 109.5 | C5—C4—H4B | 108.5 |
C11'—C10'—C9' | 121.0 (3) | H4A—C4—H4B | 107.5 |
C2'—C3'—C4'—C5' | −21.3 (4) | C16—C5—C6—C1 | −67.4 (3) |
C7'—C3'—C4'—C5' | 157.6 (2) | C4—C5—C6—C1 | 52.9 (3) |
C3'—C4'—C5'—C16' | 167.1 (2) | C10—C11—C12—C13 | −0.7 (5) |
C3'—C4'—C5'—C6' | 47.9 (3) | C11—C12—C13—C14 | 0.9 (5) |
C3'—C4'—C5'—C15' | −72.8 (3) | C5—C6—C1—O0 | 151.3 (3) |
C4'—C3'—C2'—C1' | −2.2 (4) | C5—C6—C1—C2 | −32.6 (4) |
C7'—C3'—C2'—C1' | 179.0 (2) | O0—C1—C2—C3 | 179.2 (3) |
C4'—C3'—C2'—C8 | 173.4 (2) | C6—C1—C2—C3 | 3.1 (4) |
C7'—C3'—C2'—C8 | −5.4 (4) | C7'—C8'—C7—C3 | 65.0 (3) |
C2'—C3'—C7'—O3 | −143.5 (8) | C9'—C8'—C7—C3 | −63.4 (3) |
C4'—C3'—C7'—O3 | 37.6 (8) | C7'—C8'—C7—C8 | −62.8 (3) |
C2'—C3'—C7'—C8' | −16.3 (4) | C9'—C8'—C7—C8 | 168.8 (2) |
C4'—C3'—C7'—C8' | 164.8 (2) | C11—C10—C9—C14 | 1.4 (4) |
C10'—C9'—C14'—C13' | 0.7 (4) | C11—C10—C9—C8 | −179.3 (3) |
C8'—C9'—C14'—C13' | −177.1 (3) | C3'—C2'—C8—C9 | 120.0 (3) |
O3—C7'—C8'—C9' | −55.5 (8) | C1'—C2'—C8—C9 | −64.3 (3) |
C3'—C7'—C8'—C9' | 178.4 (2) | C3'—C2'—C8—C7 | −8.5 (4) |
O3—C7'—C8'—C7 | 176.5 (8) | C1'—C2'—C8—C7 | 167.2 (2) |
C3'—C7'—C8'—C7 | 50.4 (3) | C14—C9—C8—C2' | −32.4 (4) |
C14'—C9'—C8'—C7' | −21.1 (4) | C10—C9—C8—C2' | 148.3 (2) |
C10'—C9'—C8'—C7' | 161.1 (2) | C14—C9—C8—C7 | 97.2 (3) |
C14'—C9'—C8'—C7 | 105.1 (3) | C10—C9—C8—C7 | −82.1 (3) |
C10'—C9'—C8'—C7 | −72.7 (3) | C3—C7—C8—C2' | −86.7 (3) |
C3'—C2'—C1'—O1 | 177.4 (3) | C8'—C7—C8—C2' | 41.5 (3) |
C8—C2'—C1'—O1 | 1.5 (4) | C3—C7—C8—C9 | 143.3 (2) |
C3'—C2'—C1'—C6' | −4.7 (4) | C8'—C7—C8—C9 | −88.5 (3) |
C8—C2'—C1'—C6' | 179.4 (2) | C10—C9—C14—C13 | −1.1 (4) |
C10'—C11'—C12'—C13' | 0.5 (5) | C8—C9—C14—C13 | 179.5 (3) |
C11'—C12'—C13'—C14' | −0.7 (5) | C12—C13—C14—C9 | 0.0 (4) |
C9'—C14'—C13'—C12' | 0.1 (4) | C1—C2—C3—C4 | 2.5 (4) |
O1—C1'—C6'—C5' | −147.1 (3) | C1—C2—C3—C7 | −172.2 (3) |
C2'—C1'—C6'—C5' | 35.0 (3) | C8'—C7—C3—C2 | −97.2 (3) |
C16'—C5'—C6'—C1' | −173.9 (2) | C8—C7—C3—C2 | 27.9 (4) |
C15'—C5'—C6'—C1' | 66.1 (3) | C8'—C7—C3—C4 | 87.9 (3) |
C4'—C5'—C6'—C1' | −54.6 (3) | C8—C7—C3—C4 | −147.0 (2) |
C12'—C11'—C10'—C9' | 0.3 (4) | C2—C3—C4—C5 | 21.3 (4) |
C14'—C9'—C10'—C11' | −0.9 (4) | C7—C3—C4—C5 | −163.6 (2) |
C8'—C9'—C10'—C11' | 177.0 (3) | C6—C5—C4—C3 | −47.5 (3) |
C9—C10—C11—C12 | −0.5 (4) | C15—C5—C4—C3 | −167.1 (2) |
C15—C5—C6—C1 | 172.0 (2) | C16—C5—C4—C3 | 73.0 (3) |
Experimental details
Crystal data | |
Chemical formula | C32H36O2 |
Mr | 452.61 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 170 |
a, b, c (Å) | 12.2381 (9), 21.8866 (15), 10.3089 (7) |
β (°) | 113.690 (1) |
V (Å3) | 2528.6 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.07 |
Crystal size (mm) | 0.3 × 0.15 × 0.1 |
Data collection | |
Diffractometer | CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > \2s(I)] reflections | 23714, 4484, 2142 |
Rint | 0.099 |
(sin θ/λ)max (Å−1) | 0.597 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.139, 0.94 |
No. of reflections | 4484 |
No. of parameters | 313 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.25, −0.21 |
Computer programs: SMART (Bruker, 1997a), SMART, SAINT (Bruker, 1997a), SHELXTL (Bruker, 1997b), SHELXTL.
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Two possible structures, including (Ia) without stereochemistry, were proposed for the high-melting condensation products formed in up to 59% yield from mixtures of isophorone, aromatic aldehydes, sodium hydroxide, and ethanol (Kabas, 1966). From its 1H, HSQC, and HMBC NMR spectra, the benzaldehyde product was determined to have the constitution (Ia), but the stereochemistry remained in doubt. An X-ray study has firmly established structure (Ia), including the stereochemistry. The torsion angle between HC7 and HC8 is close to 90°, showing why coupling between these protons is not observed in the NMR spectra (given as supporting information). Compound (Ia) was proposed to be formed by a sequence involving two Michael additions, but a Diels–Alder reaction of benzylideneisophorone with itself to give (II) followed by base-catalysed double-bond isomerization to (Ia) seems more likely; precedent is found in the Diels–Alder reaction of benzylideneisophorone with maleic anhydride (Kabas, 1966). Difference maps revealed a small peak at a C–O distance [1.41 (2) Å] from C7, suggesting that 10% of the sample had air-oxidized to the alcohol (Ib).