Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270103013374/ta1412sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270103013374/ta1412Isup2.hkl |
CCDC reference: 219567
A mixture of 5-hydroxy-1,4-naphthoquinone (317 mg) and 5,5-dimethyl- 3-vinyl-1,2-cyclohexadienyl acetate (350 mg) in anhydrous toluene (60 cm3) was heated under reflux for 60 h. The reaction mixture was allowed to cool to 293 K, the solvent was concentrated to 2 ml in vacuo, and the product was precipitated following dropwise addition of diethyl ether at 273 K. The product (550 mg) was purified by flash chromatography on silica eluting with hexane/diethyl ether (2:1) and was crystallized from dichloromethane/diethyl ether (1:1) to yield the title compound (yield 450 mg, 68%) as colourless crystals (m.p. 461–463 K).
H atoms were located from difference Fourier maps and refined without constraints.
Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: Xtal3.5 (Hall, King, and Stewart, 1995); program(s) used to solve structure: Xtal3.5; program(s) used to refine structure: CRYLSQ in Xtal3.5; molecular graphics: Xtal3.5; software used to prepare material for publication: BONDLA and CIFIO in Xtal3.5.
C22H22O5 | F(000) = 1552 |
Mr = 366.41 | Dx = 1.298 Mg m−3 |
Monoclinic, Cc | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: c -2yc | Cell parameters from 6110 reflections |
a = 13.774 (2) Å | θ = 2.4–20.3° |
b = 11.233 (2) Å | µ = 0.09 mm−1 |
c = 24.595 (4) Å | T = 153 K |
β = 99.792 (2)° | Fragment, colourless |
V = 3750.0 (11) Å3 | 0.32 × 0.21 × 0.17 mm |
Z = 8 |
Bruker SMART CCD diffractometer | 4771 independent reflections |
Radiation source: sealed tube | 4288 reflections with F > 2σ(F) |
Graphite monochromator | Rint = 0.044 |
ω scans | θmax = 29°, θmin = 2.4° |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | h = −18→18 |
Tmin = 0.87, Tmax = 0.96 | k = −15→15 |
21857 measured reflections | l = −32→32 |
Refinement on F | 0 restraints |
Least-squares matrix: full | 0 constraints |
R[F2 > 2σ(F2)] = 0.044 | All H-atom parameters refined |
wR(F2) = 0.046 | w = 1/(σ2(F)) + .0005F2) |
S = 1.07 | (Δ/σ)max = 0.016 |
4288 reflections | Δρmax = 0.34 e Å−3 |
661 parameters | Δρmin = −0.23 e Å−3 |
C22H22O5 | V = 3750.0 (11) Å3 |
Mr = 366.41 | Z = 8 |
Monoclinic, Cc | Mo Kα radiation |
a = 13.774 (2) Å | µ = 0.09 mm−1 |
b = 11.233 (2) Å | T = 153 K |
c = 24.595 (4) Å | 0.32 × 0.21 × 0.17 mm |
β = 99.792 (2)° |
Bruker SMART CCD diffractometer | 4771 independent reflections |
Absorption correction: multi-scan SADABS; Sheldrick, 1996 | 4288 reflections with F > 2σ(F) |
Tmin = 0.87, Tmax = 0.96 | Rint = 0.044 |
21857 measured reflections |
R[F2 > 2σ(F2)] = 0.044 | 0 restraints |
wR(F2) = 0.046 | All H-atom parameters refined |
S = 1.07 | Δρmax = 0.34 e Å−3 |
4288 reflections | Δρmin = −0.23 e Å−3 |
661 parameters |
x | y | z | Uiso*/Ueq | ||
C11 | 0.5000 (2) | 0.5573 (3) | 0.5000 (2) | 0.0258 (13) | |
O11 | 0.4053 (2) | 0.57208 (18) | 0.51478 (14) | 0.0305 (10) | |
C113 | 0.3281 (3) | 0.5156 (3) | 0.4840 (2) | 0.0360 (15) | |
O113 | 0.3347 (3) | 0.4559 (2) | 0.44397 (17) | 0.0486 (13) | |
C114 | 0.2349 (3) | 0.5388 (4) | 0.5055 (2) | 0.053 (2) | |
C12 | 0.5688 (3) | 0.5035 (3) | 0.53523 (17) | 0.0287 (14) | |
C13 | 0.6741 (3) | 0.4918 (3) | 0.52649 (17) | 0.0298 (13) | |
C131 | 0.7357 (3) | 0.5866 (4) | 0.56077 (19) | 0.0399 (18) | |
C132 | 0.7132 (3) | 0.3673 (4) | 0.5445 (2) | 0.0411 (18) | |
C14 | 0.6780 (3) | 0.5066 (3) | 0.46449 (17) | 0.0300 (14) | |
C14a | 0.6193 (3) | 0.6121 (3) | 0.43903 (16) | 0.0267 (13) | |
C15 | 0.6563 (3) | 0.6956 (3) | 0.41007 (17) | 0.0314 (14) | |
C16 | 0.5992 (3) | 0.7975 (3) | 0.38152 (17) | 0.0307 (14) | |
C16a | 0.4875 (3) | 0.7856 (3) | 0.38058 (16) | 0.0270 (13) | |
C17 | 0.4392 (3) | 0.9042 (3) | 0.36621 (17) | 0.0284 (13) | |
O17 | 0.4011 (3) | 0.9285 (2) | 0.31892 (15) | 0.0389 (11) | |
C17a | 0.4463 (3) | 0.9924 (3) | 0.41186 (17) | 0.0285 (14) | |
C18 | 0.4252 (3) | 1.1113 (3) | 0.39901 (18) | 0.0335 (15) | |
C19 | 0.4363 (3) | 1.1954 (3) | 0.44107 (19) | 0.0375 (16) | |
C110 | 0.4691 (3) | 1.1634 (3) | 0.49534 (19) | 0.0349 (17) | |
C111 | 0.4911 (3) | 1.0443 (3) | 0.50882 (17) | 0.0307 (14) | |
O111 | 0.5240 (3) | 1.0194 (2) | 0.56257 (15) | 0.0361 (11) | |
C111a | 0.4785 (3) | 0.9566 (3) | 0.46717 (17) | 0.0253 (13) | |
C112 | 0.5004 (3) | 0.8302 (3) | 0.48126 (17) | 0.0256 (13) | |
O112 | 0.5396 (3) | 0.8009 (2) | 0.52802 (15) | 0.0358 (11) | |
C112a | 0.4675 (3) | 0.7392 (3) | 0.43656 (16) | 0.0251 (13) | |
C112b | 0.5122 (3) | 0.6140 (2) | 0.44591 (16) | 0.0251 (13) | |
C21 | 0.6348 (2) | 0.3800 (3) | 0.70856 (13) | 0.0244 (13) | |
O21 | 0.7300 (2) | 0.39235 (18) | 0.69395 (14) | 0.0282 (10) | |
C213 | 0.8075 (3) | 0.3397 (3) | 0.72689 (17) | 0.0299 (14) | |
O213 | 0.8001 (2) | 0.2835 (2) | 0.76751 (15) | 0.0375 (11) | |
C214 | 0.9006 (3) | 0.3603 (4) | 0.7048 (2) | 0.045 (2) | |
C22 | 0.5671 (3) | 0.3209 (3) | 0.67421 (17) | 0.0269 (13) | |
C23 | 0.4607 (3) | 0.3111 (3) | 0.68128 (17) | 0.0300 (14) | |
C231 | 0.3988 (3) | 0.4000 (4) | 0.6425 (2) | 0.0426 (18) | |
C232 | 0.4244 (4) | 0.1838 (4) | 0.6682 (2) | 0.046 (2) | |
C24 | 0.4529 (3) | 0.3380 (3) | 0.74182 (17) | 0.0294 (14) | |
C24a | 0.5123 (3) | 0.4429 (3) | 0.76629 (16) | 0.0256 (13) | |
C25 | 0.4757 (3) | 0.5276 (3) | 0.79443 (17) | 0.0290 (14) | |
C26 | 0.5339 (3) | 0.6291 (3) | 0.82363 (17) | 0.0285 (14) | |
C26a | 0.6460 (3) | 0.6145 (3) | 0.82491 (16) | 0.0258 (13) | |
C27 | 0.6947 (3) | 0.7335 (3) | 0.83866 (17) | 0.0273 (13) | |
O27 | 0.7332 (3) | 0.7598 (2) | 0.88535 (15) | 0.0369 (11) | |
C27a | 0.6875 (3) | 0.8205 (3) | 0.79193 (17) | 0.0260 (13) | |
C28 | 0.7061 (3) | 0.9399 (3) | 0.80378 (18) | 0.0316 (15) | |
C29 | 0.6941 (3) | 1.0224 (3) | 0.76085 (19) | 0.0354 (16) | |
C210 | 0.6643 (3) | 0.9872 (3) | 0.70720 (19) | 0.0337 (16) | |
C211 | 0.6452 (3) | 0.8671 (3) | 0.69455 (17) | 0.0281 (13) | |
O211 | 0.6156 (3) | 0.8380 (2) | 0.64116 (14) | 0.0359 (11) | |
C211a | 0.6565 (3) | 0.7816 (3) | 0.73703 (17) | 0.0246 (12) | |
C212 | 0.6366 (3) | 0.6542 (3) | 0.72375 (16) | 0.0241 (12) | |
O212 | 0.6004 (3) | 0.6234 (2) | 0.67673 (14) | 0.0325 (11) | |
C212a | 0.6668 (3) | 0.5656 (2) | 0.76968 (16) | 0.0226 (12) | |
C212b | 0.6205 (3) | 0.4410 (2) | 0.76084 (16) | 0.0241 (13) | |
H12 | 0.555 (2) | 0.475 (3) | 0.5691 (15) | 0.037 (9)* | |
H131A | 0.805 (3) | 0.580 (3) | 0.5575 (15) | 0.049 (10)* | |
H131B | 0.728 (3) | 0.574 (3) | 0.6021 (16) | 0.049 (11)* | |
H131C | 0.720 (3) | 0.666 (4) | 0.5476 (17) | 0.056 (12)* | |
H132A | 0.780 (3) | 0.363 (3) | 0.5369 (14) | 0.040 (9)* | |
H132B | 0.669 (3) | 0.301 (4) | 0.520 (2) | 0.072 (14)* | |
H132C | 0.717 (3) | 0.357 (4) | 0.5881 (18) | 0.059 (12)* | |
H14A | 0.643 (3) | 0.432 (4) | 0.4466 (17) | 0.051 (10)* | |
H14B | 0.750 (3) | 0.520 (3) | 0.4590 (13) | 0.031 (8)* | |
H15 | 0.726 (3) | 0.694 (3) | 0.4062 (14) | 0.041 (9)* | |
H16aA | 0.612 (2) | 0.805 (3) | 0.3414 (14) | 0.033 (9)* | |
H16B | 0.625 (3) | 0.875 (3) | 0.3996 (15) | 0.041 (10)* | |
H16aA | 0.460 (2) | 0.730 (3) | 0.3534 (13) | 0.022 (7)* | |
H18 | 0.401 (2) | 1.138 (3) | 0.3584 (13) | 0.025 (8)* | |
H19 | 0.418 (3) | 1.282 (3) | 0.4304 (15) | 0.042 (9)* | |
H110 | 0.474 (3) | 1.217 (4) | 0.5235 (17) | 0.055 (12)* | |
H111 | 0.540 (4) | 0.943 (5) | 0.564 (2) | 0.086 (17)* | |
H112A | 0.401 (2) | 0.738 (3) | 0.4378 (12) | 0.020 (7)* | |
H112B | 0.477 (2) | 0.563 (3) | 0.4158 (13) | 0.024 (8)* | |
H114A | 0.246 (3) | 0.576 (4) | 0.5436 (19) | 0.057 (12)* | |
H114B | 0.203 (4) | 0.470 (5) | 0.510 (2) | 0.079 (16)* | |
H114C | 0.190 (5) | 0.596 (6) | 0.480 (3) | 0.15 (3)* | |
H22 | 0.588 (2) | 0.290 (3) | 0.6416 (12) | 0.017 (7)* | |
H231A | 0.332 (3) | 0.387 (4) | 0.6473 (18) | 0.067 (13)* | |
H231B | 0.403 (3) | 0.387 (4) | 0.6013 (18) | 0.053 (11)* | |
H231C | 0.421 (3) | 0.491 (4) | 0.6515 (16) | 0.042 (10)* | |
H232A | 0.354 (3) | 0.172 (3) | 0.6767 (16) | 0.058 (12)* | |
H232B | 0.466 (4) | 0.125 (5) | 0.694 (2) | 0.096 (19)* | |
H232C | 0.427 (3) | 0.163 (3) | 0.6301 (18) | 0.056 (11)* | |
H24A | 0.475 (3) | 0.262 (3) | 0.7641 (16) | 0.047 (10)* | |
H24B | 0.386 (3) | 0.344 (3) | 0.7475 (13) | 0.031 (8)* | |
H25 | 0.410 (2) | 0.526 (3) | 0.7962 (12) | 0.024 (7)* | |
H26aA | 0.525 (3) | 0.636 (3) | 0.8622 (15) | 0.035 (9)* | |
H26B | 0.512 (2) | 0.706 (3) | 0.8060 (13) | 0.030 (8)* | |
H26aA | 0.671 (2) | 0.555 (3) | 0.8541 (14) | 0.028 (8)* | |
H28 | 0.731 (2) | 0.970 (3) | 0.8403 (13) | 0.023 (7)* | |
H29 | 0.708 (3) | 1.101 (3) | 0.7677 (14) | 0.034 (9)* | |
H210 | 0.653 (2) | 1.042 (3) | 0.6772 (14) | 0.032 (9)* | |
H211 | 0.602 (3) | 0.758 (4) | 0.6397 (14) | 0.041 (10)* | |
H212A | 0.740 (2) | 0.556 (3) | 0.7730 (13) | 0.030 (8)* | |
H212B | 0.653 (2) | 0.392 (3) | 0.7933 (13) | 0.026 (8)* | |
H214A | 0.951 (3) | 0.398 (4) | 0.7363 (18) | 0.061 (12)* | |
H214B | 0.892 (3) | 0.397 (4) | 0.672 (2) | 0.068 (15)* | |
H214C | 0.923 (4) | 0.283 (6) | 0.697 (2) | 0.11 (2)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C11 | 0.0214 (13) | 0.0299 (15) | 0.0269 (15) | −0.0011 (11) | 0.0065 (11) | −0.0005 (12) |
O11 | 0.0243 (9) | 0.0349 (11) | 0.0335 (11) | −0.0019 (8) | 0.0079 (8) | 0.0023 (9) |
C113 | 0.0255 (14) | 0.0257 (15) | 0.057 (2) | 0.0003 (12) | 0.0075 (14) | 0.0033 (14) |
O113 | 0.0338 (12) | 0.0396 (13) | 0.0713 (18) | −0.0028 (10) | 0.0056 (11) | −0.0172 (13) |
C114 | 0.0258 (17) | 0.049 (2) | 0.085 (3) | −0.0029 (16) | 0.0183 (19) | −0.002 (2) |
C12 | 0.0312 (15) | 0.0339 (16) | 0.0216 (14) | −0.0014 (12) | 0.0061 (11) | 0.0011 (12) |
C13 | 0.0275 (13) | 0.0401 (16) | 0.0216 (13) | 0.0050 (13) | 0.0038 (10) | 0.0022 (12) |
C131 | 0.0258 (15) | 0.065 (2) | 0.0284 (17) | −0.0019 (15) | 0.0025 (12) | −0.0074 (16) |
C132 | 0.0381 (18) | 0.052 (2) | 0.0345 (18) | 0.0145 (16) | 0.0099 (14) | 0.0116 (16) |
C14 | 0.0286 (14) | 0.0396 (18) | 0.0219 (14) | 0.0072 (13) | 0.0047 (11) | −0.0004 (12) |
C14a | 0.0275 (13) | 0.0355 (15) | 0.0169 (13) | 0.0044 (12) | 0.0033 (10) | −0.0033 (11) |
C15 | 0.0259 (14) | 0.0444 (18) | 0.0247 (14) | 0.0054 (13) | 0.0061 (11) | 0.0006 (13) |
C16 | 0.0312 (14) | 0.0367 (17) | 0.0265 (15) | 0.0015 (13) | 0.0113 (12) | 0.0035 (13) |
C16a | 0.0293 (14) | 0.0338 (15) | 0.0168 (13) | −0.0001 (12) | 0.0007 (11) | −0.0010 (12) |
C17 | 0.0219 (13) | 0.0376 (16) | 0.0255 (14) | 0.0009 (12) | 0.0033 (11) | 0.0053 (12) |
O17 | 0.0377 (12) | 0.0489 (14) | 0.0265 (11) | 0.0056 (10) | −0.0047 (9) | 0.0074 (10) |
C17a | 0.0218 (13) | 0.0360 (16) | 0.0280 (15) | 0.0028 (11) | 0.0049 (11) | 0.0034 (13) |
C18 | 0.0295 (15) | 0.0373 (17) | 0.0353 (18) | 0.0041 (13) | 0.0099 (13) | 0.0069 (14) |
C19 | 0.0339 (16) | 0.0347 (17) | 0.047 (2) | 0.0072 (13) | 0.0152 (14) | 0.0080 (15) |
C110 | 0.0390 (18) | 0.0304 (17) | 0.0384 (19) | 0.0024 (14) | 0.0154 (14) | −0.0035 (14) |
C111 | 0.0290 (14) | 0.0385 (16) | 0.0262 (15) | 0.0020 (12) | 0.0090 (12) | 0.0003 (13) |
O111 | 0.0466 (13) | 0.0356 (13) | 0.0256 (11) | 0.0037 (10) | 0.0046 (9) | −0.0053 (9) |
C111a | 0.0216 (12) | 0.0277 (14) | 0.0274 (14) | 0.0026 (11) | 0.0065 (11) | 0.0012 (11) |
C112 | 0.0223 (13) | 0.0315 (15) | 0.0239 (14) | 0.0027 (11) | 0.0070 (11) | 0.0004 (12) |
O112 | 0.0469 (13) | 0.0349 (12) | 0.0229 (10) | 0.0030 (10) | −0.0020 (9) | −0.0001 (9) |
C112a | 0.0222 (12) | 0.0320 (15) | 0.0205 (13) | 0.0011 (11) | 0.0024 (10) | 0.0000 (11) |
C112b | 0.0271 (14) | 0.0294 (15) | 0.0181 (14) | 0.0005 (11) | 0.0021 (11) | −0.0020 (11) |
C21 | 0.0233 (14) | 0.0264 (15) | 0.0234 (14) | 0.0013 (11) | 0.0044 (11) | 0.0019 (11) |
O21 | 0.0239 (9) | 0.0342 (11) | 0.0269 (10) | 0.0006 (8) | 0.0055 (8) | 0.0003 (8) |
C213 | 0.0276 (14) | 0.0251 (14) | 0.0354 (16) | −0.0018 (11) | 0.0007 (12) | −0.0057 (12) |
O213 | 0.0346 (11) | 0.0341 (11) | 0.0414 (13) | 0.0016 (9) | −0.0006 (9) | 0.0075 (10) |
C214 | 0.0296 (17) | 0.049 (2) | 0.058 (2) | 0.0037 (16) | 0.0089 (17) | 0.007 (2) |
C22 | 0.0274 (13) | 0.0317 (15) | 0.0221 (14) | −0.0004 (12) | 0.0061 (11) | −0.0000 (11) |
C23 | 0.0264 (13) | 0.0422 (17) | 0.0214 (13) | −0.0074 (13) | 0.0036 (11) | −0.0054 (12) |
C231 | 0.0278 (16) | 0.068 (3) | 0.0312 (18) | 0.0021 (16) | 0.0030 (13) | 0.0070 (17) |
C232 | 0.044 (2) | 0.059 (2) | 0.037 (2) | −0.0233 (18) | 0.0110 (16) | −0.0179 (18) |
C24 | 0.0298 (15) | 0.0377 (17) | 0.0217 (14) | −0.0104 (13) | 0.0072 (11) | −0.0044 (12) |
C24a | 0.0249 (13) | 0.0339 (15) | 0.0185 (13) | −0.0042 (11) | 0.0048 (10) | 0.0019 (11) |
C25 | 0.0255 (14) | 0.0386 (16) | 0.0238 (14) | −0.0038 (12) | 0.0067 (11) | −0.0022 (12) |
C26 | 0.0279 (14) | 0.0346 (16) | 0.0246 (14) | −0.0018 (12) | 0.0090 (12) | −0.0060 (12) |
C26a | 0.0286 (13) | 0.0290 (14) | 0.0196 (13) | −0.0020 (11) | 0.0038 (11) | −0.0011 (11) |
C27 | 0.0215 (12) | 0.0336 (15) | 0.0265 (14) | 0.0013 (11) | 0.0033 (11) | −0.0042 (12) |
O27 | 0.0392 (12) | 0.0429 (13) | 0.0259 (11) | −0.0037 (10) | −0.0026 (9) | −0.0085 (9) |
C27a | 0.0217 (13) | 0.0285 (14) | 0.0282 (15) | −0.0030 (11) | 0.0056 (11) | −0.0042 (12) |
C28 | 0.0304 (15) | 0.0353 (17) | 0.0301 (17) | −0.0053 (13) | 0.0080 (12) | −0.0082 (13) |
C29 | 0.0389 (17) | 0.0254 (15) | 0.045 (2) | −0.0076 (13) | 0.0150 (14) | −0.0053 (13) |
C210 | 0.0336 (16) | 0.0308 (16) | 0.0387 (18) | −0.0007 (13) | 0.0122 (14) | 0.0054 (14) |
C211 | 0.0262 (13) | 0.0302 (15) | 0.0290 (15) | −0.0003 (11) | 0.0078 (12) | 0.0010 (12) |
O211 | 0.0477 (13) | 0.0326 (12) | 0.0266 (12) | −0.0018 (10) | 0.0042 (10) | 0.0021 (9) |
C211a | 0.0217 (12) | 0.0301 (14) | 0.0219 (14) | −0.0012 (11) | 0.0036 (10) | −0.0005 (11) |
C212 | 0.0205 (12) | 0.0306 (15) | 0.0217 (13) | 0.0001 (11) | 0.0048 (10) | −0.0003 (11) |
O212 | 0.0419 (12) | 0.0324 (12) | 0.0213 (10) | −0.0042 (9) | 0.0001 (9) | −0.0002 (8) |
C212a | 0.0212 (12) | 0.0273 (14) | 0.0191 (13) | −0.0009 (10) | 0.0026 (10) | −0.0018 (11) |
C212b | 0.0249 (13) | 0.0262 (14) | 0.0207 (14) | 0.0010 (11) | 0.0020 (11) | −0.0007 (11) |
C11—O11 | 1.422 (3) | C21—O21 | 1.424 (5) |
C11—C12 | 1.317 (4) | C21—C22 | 1.325 (4) |
C11—C112b | 1.510 (4) | C21—C212b | 1.499 (5) |
O11—C113 | 1.354 (5) | O21—C213 | 1.361 (5) |
C113—O113 | 1.207 (6) | C213—O213 | 1.200 (5) |
C113—C114 | 1.494 (7) | C213—C214 | 1.493 (6) |
C114—H114A | 1.01 (5) | C214—H214A | 1.04 (4) |
C114—H114B | 0.91 (6) | C214—H214B | 0.90 (5) |
C114—H114C | 1.02 (7) | C214—H214C | 0.95 (7) |
C12—C13 | 1.508 (6) | C22—C23 | 1.509 (6) |
C12—H12 | 0.94 (4) | C22—H22 | 0.96 (3) |
C13—C131 | 1.525 (5) | C23—C231 | 1.535 (5) |
C13—C132 | 1.536 (5) | C23—C232 | 1.531 (5) |
C13—C14 | 1.544 (6) | C23—C24 | 1.541 (6) |
C131—H131A | 0.97 (4) | C231—H231A | 0.96 (5) |
C131—H131B | 1.05 (4) | C231—H231B | 1.03 (4) |
C131—H131C | 0.97 (4) | C231—H231C | 1.08 (4) |
C132—H132A | 0.97 (4) | C232—H232A | 1.04 (5) |
C132—H132B | 1.08 (5) | C232—H232B | 1.03 (5) |
C132—H132C | 1.07 (4) | C232—H232C | 0.97 (4) |
C14—C14a | 1.509 (5) | C24—C24a | 1.501 (5) |
C14—H14A | 1.02 (4) | C24—H24A | 1.04 (4) |
C14—H14B | 1.03 (4) | C24—H24B | 0.95 (4) |
C14a—C15 | 1.330 (5) | C24a—C25 | 1.325 (5) |
C14a—C112b | 1.515 (6) | C24a—C212b | 1.519 (6) |
C15—C16 | 1.496 (5) | C25—C26 | 1.505 (5) |
C15—H15 | 0.98 (4) | C25—H25 | 0.92 (3) |
C16—C16a | 1.541 (6) | C26—C26a | 1.549 (6) |
C16—H16aA | 1.03 (4) | C26—H26aA | 0.98 (4) |
C16—H16B | 1.02 (4) | C26—H26B | 0.99 (3) |
C16a—C17 | 1.504 (5) | C26a—C27 | 1.508 (4) |
C16a—C112a | 1.540 (6) | C26a—C212a | 1.536 (6) |
C16a—H16aA | 0.95 (3) | C26a—H26aA | 1.00 (3) |
C17—O17 | 1.223 (5) | C27—O27 | 1.217 (5) |
C17—C17a | 1.488 (5) | C27—C27a | 1.499 (5) |
C17a—C18 | 1.392 (5) | C27a—C28 | 1.387 (4) |
C17a—C111a | 1.415 (6) | C27a—C211a | 1.415 (5) |
C18—C19 | 1.390 (6) | C28—C29 | 1.393 (6) |
C18—H18 | 1.04 (3) | C28—H28 | 0.97 (3) |
C19—C110 | 1.382 (6) | C29—C210 | 1.372 (6) |
C19—H19 | 1.02 (4) | C29—H29 | 0.92 (4) |
C110—C111 | 1.399 (5) | C210—C211 | 1.399 (4) |
C110—H110 | 0.91 (4) | C210—H210 | 0.95 (3) |
C111—O111 | 1.352 (5) | C211—O211 | 1.347 (5) |
C111—C111a | 1.410 (5) | C211—C211a | 1.409 (5) |
O111—H111 | 0.88 (6) | O211—H211 | 0.92 (4) |
C111a—C112 | 1.480 (4) | C211a—C212 | 1.482 (4) |
C112—O112 | 1.229 (5) | C212—O212 | 1.229 (5) |
C112—C112a | 1.513 (5) | C212—C212a | 1.510 (5) |
C112a—C112b | 1.537 (4) | C212a—C212b | 1.538 (4) |
C112a—H112A | 0.93 (3) | C212a—H212A | 1.00 (3) |
C112b—H112B | 1.00 (3) | C212b—H212B | 1.01 (3) |
O11—C11—C12 | 118.3 (2) | O21—C21—C22 | 117.8 (3) |
O11—C11—C112b | 114.8 (2) | O21—C21—C212b | 115.7 (3) |
C12—C11—C112b | 126.7 (2) | C22—C21—C212b | 126.5 (3) |
C11—O11—C113 | 118.0 (3) | C21—O21—C213 | 118.1 (3) |
O11—C113—O113 | 123.8 (4) | O21—C213—O213 | 123.7 (4) |
O11—C113—C114 | 111.1 (4) | O21—C213—C214 | 110.6 (4) |
O113—C113—C114 | 125.1 (4) | O213—C213—C214 | 125.7 (4) |
C113—C114—H114A | 113 (2) | C213—C214—H214A | 107 (3) |
C113—C114—H114B | 112 (3) | C213—C214—H214B | 114 (3) |
C113—C114—H114C | 111 (4) | C213—C214—H214C | 105 (4) |
H114A—C114—H114B | 103 (4) | H214A—C214—H214B | 117 (4) |
H114A—C114—H114C | 106 (5) | H214A—C214—H214C | 109 (4) |
H114B—C114—H114C | 111 (5) | H214B—C214—H214C | 103 (5) |
C11—C12—C13 | 123.2 (3) | C21—C22—C23 | 123.7 (4) |
C11—C12—H12 | 121 (2) | C21—C22—H22 | 115.6 (16) |
C13—C12—H12 | 116 (2) | C23—C22—H22 | 120.4 (16) |
C12—C13—C131 | 108.6 (3) | C22—C23—C231 | 109.2 (3) |
C12—C13—C132 | 109.7 (3) | C22—C23—C232 | 109.4 (3) |
C12—C13—C14 | 109.1 (3) | C22—C23—C24 | 109.0 (3) |
C131—C13—C132 | 110.0 (3) | C231—C23—C232 | 110.5 (3) |
C131—C13—C14 | 111.2 (3) | C231—C23—C24 | 110.5 (3) |
C132—C13—C14 | 108.3 (3) | C232—C23—C24 | 108.2 (3) |
C13—C131—H131A | 111 (2) | C23—C231—H231A | 105 (3) |
C13—C131—H131B | 108 (2) | C23—C231—H231B | 114 (2) |
C13—C131—H131C | 113 (2) | C23—C231—H231C | 112.5 (19) |
H131A—C131—H131B | 109 (3) | H231A—C231—H231B | 108 (3) |
H131A—C131—H131C | 102 (3) | H231A—C231—H231C | 111 (3) |
H131B—C131—H131C | 113 (3) | H231B—C231—H231C | 106 (3) |
C13—C132—H132A | 106 (2) | C23—C232—H232A | 111 (2) |
C13—C132—H132B | 109 (2) | C23—C232—H232B | 110 (3) |
C13—C132—H132C | 110 (2) | C23—C232—H232C | 111 (2) |
H132A—C132—H132B | 109 (3) | H232A—C232—H232B | 104 (4) |
H132A—C132—H132C | 108 (3) | H232A—C232—H232C | 111 (3) |
H132B—C132—H132C | 114 (3) | H232B—C232—H232C | 110 (4) |
C13—C14—C14a | 112.9 (3) | C23—C24—C24a | 114.8 (3) |
C13—C14—H14A | 104 (2) | C23—C24—H24A | 107 (2) |
C13—C14—H14B | 109.9 (18) | C23—C24—H24B | 113 (2) |
C14a—C14—H14A | 107 (2) | C24a—C24—H24A | 110 (2) |
C14a—C14—H14B | 106.9 (18) | C24a—C24—H24B | 111 (2) |
H14A—C14—H14B | 117 (3) | H24A—C24—H24B | 101 (3) |
C14—C14a—C15 | 123.3 (4) | C24—C24a—C25 | 122.9 (4) |
C14—C14a—C112b | 115.4 (3) | C24—C24a—C212b | 115.4 (3) |
C15—C14a—C112b | 121.3 (3) | C25—C24a—C212b | 121.5 (3) |
C14a—C15—C16 | 124.9 (4) | C24a—C25—C26 | 125.0 (4) |
C14a—C15—H15 | 121 (2) | C24a—C25—H25 | 118.5 (19) |
C16—C15—H15 | 114 (2) | C26—C25—H25 | 116.5 (19) |
C15—C16—C16a | 112.6 (3) | C25—C26—C26a | 112.2 (3) |
C15—C16—H16aA | 110.6 (18) | C25—C26—H26aA | 112 (2) |
C15—C16—H16B | 109 (2) | C25—C26—H26B | 110.8 (18) |
C16a—C16—H16aA | 108.8 (18) | C26a—C26—H26aA | 106 (2) |
C16a—C16—H16B | 111 (2) | C26a—C26—H26B | 109 (2) |
H16aA—C16—H16B | 104 (3) | H26aA—C26—H26B | 106 (3) |
C16—C16a—C17 | 109.1 (3) | C26—C26a—C27 | 108.3 (3) |
C16—C16a—C112a | 110.2 (3) | C26—C26a—C212a | 110.8 (3) |
C16—C16a—H16aA | 111 (2) | C26—C26a—H26aA | 108 (2) |
C17—C16a—C112a | 111.7 (3) | C27—C26a—C212a | 111.9 (3) |
C17—C16a—H16aA | 107.9 (18) | C27—C26a—H26aA | 110.1 (18) |
C112a—C16a—H16aA | 107 (2) | C212a—C26a—H26aA | 108 (2) |
C16a—C17—O17 | 121.5 (3) | C26a—C27—O27 | 122.2 (3) |
C16a—C17—C17a | 116.3 (3) | C26a—C27—C27a | 115.9 (3) |
O17—C17—C17a | 122.1 (3) | O27—C27—C27a | 121.8 (3) |
C17—C17a—C18 | 118.9 (4) | C27—C27a—C28 | 118.9 (3) |
C17—C17a—C111a | 120.4 (3) | C27—C27a—C211a | 120.0 (3) |
C18—C17a—C111a | 120.7 (3) | C28—C27a—C211a | 121.0 (3) |
C17a—C18—C19 | 119.4 (4) | C27a—C28—C29 | 119.3 (4) |
C17a—C18—H18 | 120.9 (17) | C27a—C28—H28 | 123.8 (18) |
C19—C18—H18 | 119.7 (17) | C29—C28—H28 | 116.8 (18) |
C18—C19—C110 | 121.2 (3) | C28—C29—C210 | 121.0 (3) |
C18—C19—H19 | 117 (2) | C28—C29—H29 | 121 (2) |
C110—C19—H19 | 121 (2) | C210—C29—H29 | 118 (2) |
C19—C110—C111 | 120.0 (4) | C29—C210—C211 | 120.4 (4) |
C19—C110—H110 | 122 (3) | C29—C210—H210 | 123 (2) |
C111—C110—H110 | 118 (3) | C211—C210—H210 | 117 (2) |
C110—C111—O111 | 116.9 (3) | C210—C211—O211 | 117.7 (3) |
C110—C111—C111a | 120.0 (4) | C210—C211—C211a | 120.0 (4) |
O111—C111—C111a | 123.1 (3) | O211—C211—C211a | 122.3 (3) |
C111—O111—H111 | 107 (3) | C211—O211—H211 | 108 (2) |
C17a—C111a—C111 | 118.7 (3) | C27a—C211a—C211 | 118.3 (3) |
C17a—C111a—C112 | 121.0 (3) | C27a—C211a—C212 | 121.6 (3) |
C111—C111a—C112 | 120.3 (3) | C211—C211a—C212 | 120.1 (3) |
C111a—C112—O112 | 121.0 (3) | C211a—C212—O212 | 120.6 (3) |
C111a—C112—C112a | 117.0 (3) | C211a—C212—C212a | 117.0 (3) |
O112—C112—C112a | 121.9 (3) | O212—C212—C212a | 122.3 (3) |
C16a—C112a—C112 | 110.1 (3) | C26a—C212a—C212 | 110.9 (3) |
C16a—C112a—C112b | 108.4 (3) | C26a—C212a—C212b | 108.4 (3) |
C16a—C112a—H112A | 111.3 (18) | C26a—C212a—H212A | 107.7 (18) |
C112—C112a—C112b | 116.5 (3) | C212—C212a—C212b | 116.0 (3) |
C112—C112a—H112A | 99.1 (18) | C212—C212a—H212A | 106.3 (19) |
C112b—C112a—H112A | 111.2 (18) | C212b—C212a—H212A | 107.2 (19) |
C11—C112b—C14a | 110.4 (3) | C21—C212b—C24a | 110.9 (3) |
C11—C112b—C112a | 114.6 (3) | C21—C212b—C212a | 115.1 (3) |
C11—C112b—H112B | 107.4 (19) | C21—C212b—H212B | 109 (2) |
C14a—C112b—C112a | 111.7 (3) | C24a—C212b—C212a | 111.4 (3) |
C14a—C112b—H112B | 106 (2) | C24a—C212b—H212B | 105 (2) |
C112a—C112b—H112B | 106.2 (17) | C212a—C212b—H212B | 105.2 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O111—H111···O112 | 0.88 (6) | 1.83 (5) | 2.618 (4) | 148 (4) |
O211—H211···O212 | 0.92 (4) | 1.77 (4) | 2.586 (4) | 147 (3) |
Experimental details
Crystal data | |
Chemical formula | C22H22O5 |
Mr | 366.41 |
Crystal system, space group | Monoclinic, Cc |
Temperature (K) | 153 |
a, b, c (Å) | 13.774 (2), 11.233 (2), 24.595 (4) |
β (°) | 99.792 (2) |
V (Å3) | 3750.0 (11) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.32 × 0.21 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART CCD diffractometer |
Absorption correction | Multi-scan SADABS; Sheldrick, 1996 |
Tmin, Tmax | 0.87, 0.96 |
No. of measured, independent and observed [F > 2σ(F)] reflections | 21857, 4771, 4288 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.682 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.044, 0.046, 1.07 |
No. of reflections | 4288 |
No. of parameters | 661 |
H-atom treatment | All H-atom parameters refined |
Δρmax, Δρmin (e Å−3) | 0.34, −0.23 |
Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), Xtal3.5 (Hall, King, and Stewart, 1995), CRYLSQ in Xtal3.5, BONDLA and CIFIO in Xtal3.5.
D—H···A | D—H | H···A | D···A | D—H···A |
O111—H111···O112 | 0.88 (6) | 1.83 (5) | 2.618 (4) | 148 (4) |
O211—H211···O212 | 0.92 (4) | 1.77 (4) | 2.586 (4) | 147 (3) |
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The results of the low-temperature single-crystal X-ray study as presented in Figs. 1 and 2 and Tables 1 and 2 are consistent with the given formulation, stoichiometry and stereochemistry. Although non-centrosymmetric, the individual crystals are racemic; the asymmetric unit of the structure consists of two independent molecules of similar geometry and conformation, with an interesting pseudosymmetry evident in their packing (Figs. 1 and 2). The fused tetracyclic ring system (ring 'D') has been recorded previously with diverse combinations of hydroxy and keto moieties at the 7,12-sites, with phenol substituents at the 8- rather than the 11-position as in the title compound, and with a diversity of double-bond and/or epoxide functionalities variously associated with rings A and B. A brominated adduct (Rozek et al., 2001) corresponding to the present combination of substituents has also been reported (see Kim et al., 1992; Rozek, Janowski et al., 1998; Rozek, Tiekink et al., 1998; Sasaki et al., 1998.; Apponyi et al., 2002). The combination of ring fusions and functionalities results in a curved/'dished' molecule with dihedral angles between the planes of the double bonds about Cn1—Cn2 and Cn5—Cn6 of 29.7 (1) and 27.7 (2)° (n = 1 or 2), the angles to the aromatic ring being, respectively, 84.8 (2) and 85.8 (2), and 75.6 (1) and 76.6 (1)°; the pendant C2O2 acetate planes are twisted to lie at dihedral angles of 115.4 (2) and 115.3 (2)° to the Cn1—Cn2 environment planes. Hydrogen-bonding details are given in the Table 1. A pronounced asymmetry in the exocyclic angles at Cn11, suggestive of O···O repulsion, is more pronounced than at Cn12 (or Cn7).