3'-Isopropyl-8',8'-dimethyl-2-benzofuran-1-spiro-7'-bicyclo[4.2.0]octa-1'(6'),2',4'-trien-3-one
Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680402940X/lh6311sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680402940X/lh63112sup2.hkl |
CCDC reference: 259602
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2003); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 2001); software used to prepare material for publication: SHELXTL.
C20H20O2 | F(000) = 624 |
Mr = 292.36 | Dx = 1.223 Mg m−3 |
Monoclinic, P21/c | Melting point = 377–378 K |
Hall symbol: -P 2ybc | Mo Kα radiation, λ = 0.71073 Å |
a = 11.8742 (4) Å | Cell parameters from 6130 reflections |
b = 10.0738 (3) Å | θ = 2.5–27.0° |
c = 13.3550 (4) Å | µ = 0.08 mm−1 |
β = 96.375 (1)° | T = 150 K |
V = 1587.62 (9) Å3 | Block, colorless |
Z = 4 | 0.24 × 0.20 × 0.17 mm |
Bruker SMART6000 PLATFORM CCD area-detector diffractometer | 3496 independent reflections |
Radiation source: sealed tube | 2920 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 27.1°, θmin = 2.5° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2001) | h = −15→15 |
Tmin = 0.922, Tmax = 0.987 | k = −12→12 |
11970 measured reflections | l = −14→17 |
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)] = 0.060 | Hydrogen site location: mixed |
wR(F2) = 0.130 | H-atom parameters constrained |
S = 1.12 | w = 1/[σ2(Fo2) + (0.0291P)2 + 1.3492P] where P = (Fo2 + 2Fc2)/3 |
3496 reflections | (Δ/σ)max < 0.001 |
199 parameters | Δρmax = 0.34 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
Experimental. Single crystals were obtained from pentane. A suitable crystal was mounted on the tip of a glass fiber with paratone-N. The first 50 frames of data were recollected for a decay correction. The decay correction was applied simultaneously with the absorption correction in SADABS. No formal measure of the extent of decay is printed out by this program. The final unit cell is obtained from the refinement of the XYZ weighted centroids of reflections above 20 σ(I). Note that the absorption correction parameters Tmin and Tmax also reflect beam corrections, etc. As a result, the numerical values for Tmin and Tmax may differ from expected values based solely absorption effects and crystal size. Spectroscopic details: IR (neat) 2961, 2869, 1760, 1466, 1230 cm-1. 1H NMR (250 MHz, CDCl3) δ 7.9 (d, 1H), 7.5 (m, 2H), 7.1 (m, 3H), 6.9 (d, 1H), 3.0 (septet, 1H), 1.29 (s, 6H), 1.26 (d, 6H) p.p.m.. 13C NMR (60 MHz, CDCl3) δ 170.5, 152.5, 149.0, 138.3, 133.2, 129.1, 127.2, 126.4, 125.2, 124.0, 122.8, 118.2, 92.1, 55.9, 35.0, 24.1, 23.7 p.p.m.. GC—MS m/z (rel. intensity): 292 (M+, 5), 249 (50), 221 (100). HRMS calcd. for C20H21O2 [M+H]+, 293.1542, found 293.1536. |
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 out to 0.78 Å. 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 | 0.31294 (11) | 0.48730 (13) | 0.13950 (10) | 0.0232 (3) | |
O2 | 0.15109 (12) | 0.57151 (14) | 0.06357 (10) | 0.0297 (3) | |
C2 | 0.20896 (15) | 0.47580 (19) | 0.08549 (13) | 0.0218 (4) | |
C3 | 0.18921 (15) | 0.33482 (19) | 0.06196 (13) | 0.0220 (4) | |
C4 | 0.09866 (16) | 0.2752 (2) | 0.00330 (15) | 0.0275 (4) | |
H4 | 0.0357 | 0.3256 | −0.0258 | 0.033* | |
C5 | 0.10453 (18) | 0.1399 (2) | −0.01060 (15) | 0.0321 (5) | |
H5 | 0.0444 | 0.0957 | −0.0501 | 0.038* | |
C6 | 0.19710 (18) | 0.0671 (2) | 0.03238 (15) | 0.0302 (5) | |
H6 | 0.1988 | −0.0261 | 0.0218 | 0.036* | |
C7 | 0.28713 (16) | 0.1274 (2) | 0.09035 (14) | 0.0251 (4) | |
H7 | 0.3504 | 0.0772 | 0.1188 | 0.030* | |
C8 | 0.28157 (15) | 0.26304 (19) | 0.10527 (13) | 0.0202 (4) | |
C9 | 0.36430 (15) | 0.35744 (18) | 0.16087 (13) | 0.0193 (4) | |
C10 | 0.48861 (15) | 0.34957 (18) | 0.14576 (13) | 0.0198 (4) | |
C11 | 0.56400 (16) | 0.35548 (19) | 0.07372 (14) | 0.0228 (4) | |
H11 | 0.5397 | 0.3709 | 0.0045 | 0.027* | |
C12 | 0.67733 (16) | 0.33744 (19) | 0.10931 (14) | 0.0238 (4) | |
H12 | 0.7320 | 0.3407 | 0.0625 | 0.029* | |
C13 | 0.71483 (15) | 0.31457 (18) | 0.21137 (14) | 0.0214 (4) | |
C14 | 0.63644 (15) | 0.30620 (18) | 0.28176 (13) | 0.0202 (4) | |
H14 | 0.6594 | 0.2884 | 0.3509 | 0.024* | |
C15 | 0.52366 (15) | 0.32507 (17) | 0.24594 (14) | 0.0194 (4) | |
C16 | 0.40471 (15) | 0.33613 (19) | 0.27923 (13) | 0.0207 (4) | |
C17 | 0.84104 (15) | 0.3022 (2) | 0.24444 (15) | 0.0253 (4) | |
H17 | 0.8510 | 0.2861 | 0.3188 | 0.030* | |
C18 | 0.89344 (18) | 0.1857 (2) | 0.1939 (2) | 0.0422 (6) | |
H18A | 0.8592 | 0.1027 | 0.2141 | 0.063* | |
H18B | 0.9753 | 0.1836 | 0.2144 | 0.063* | |
H18C | 0.8796 | 0.1956 | 0.1205 | 0.063* | |
C19 | 0.90337 (17) | 0.4303 (2) | 0.22424 (18) | 0.0332 (5) | |
H19A | 0.9831 | 0.4224 | 0.2516 | 0.050* | |
H19B | 0.8687 | 0.5048 | 0.2567 | 0.050* | |
H19C | 0.8983 | 0.4459 | 0.1515 | 0.050* | |
C20 | 0.39013 (17) | 0.4606 (2) | 0.34184 (15) | 0.0278 (4) | |
H20A | 0.3100 | 0.4716 | 0.3511 | 0.042* | |
H20B | 0.4163 | 0.5383 | 0.3068 | 0.042* | |
H20C | 0.4348 | 0.4517 | 0.4077 | 0.042* | |
C21 | 0.35664 (17) | 0.2144 (2) | 0.32678 (15) | 0.0282 (4) | |
H21A | 0.2746 | 0.2249 | 0.3270 | 0.042* | |
H21B | 0.3923 | 0.2045 | 0.3961 | 0.042* | |
H21C | 0.3720 | 0.1353 | 0.2878 | 0.042* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0214 (7) | 0.0205 (7) | 0.0265 (7) | 0.0024 (5) | −0.0019 (5) | 0.0027 (5) |
O2 | 0.0275 (7) | 0.0306 (8) | 0.0306 (8) | 0.0115 (6) | 0.0019 (6) | 0.0050 (6) |
C2 | 0.0193 (9) | 0.0280 (10) | 0.0185 (9) | 0.0039 (8) | 0.0041 (7) | 0.0045 (7) |
C3 | 0.0186 (9) | 0.0280 (10) | 0.0198 (9) | 0.0017 (8) | 0.0040 (7) | 0.0022 (7) |
C4 | 0.0176 (9) | 0.0403 (12) | 0.0242 (10) | −0.0003 (8) | 0.0000 (7) | 0.0045 (9) |
C5 | 0.0266 (10) | 0.0421 (13) | 0.0271 (10) | −0.0120 (9) | 0.0007 (8) | −0.0042 (9) |
C6 | 0.0347 (11) | 0.0262 (11) | 0.0302 (11) | −0.0057 (9) | 0.0061 (9) | −0.0014 (8) |
C7 | 0.0249 (10) | 0.0251 (10) | 0.0252 (10) | 0.0018 (8) | 0.0021 (8) | 0.0019 (8) |
C8 | 0.0175 (9) | 0.0259 (10) | 0.0175 (8) | −0.0007 (7) | 0.0035 (7) | 0.0035 (7) |
C9 | 0.0179 (9) | 0.0195 (9) | 0.0201 (9) | 0.0011 (7) | −0.0003 (7) | 0.0033 (7) |
C10 | 0.0185 (9) | 0.0177 (9) | 0.0220 (9) | −0.0009 (7) | −0.0029 (7) | 0.0014 (7) |
C11 | 0.0241 (9) | 0.0251 (10) | 0.0188 (9) | −0.0025 (8) | 0.0008 (7) | 0.0014 (7) |
C12 | 0.0212 (9) | 0.0241 (10) | 0.0272 (10) | −0.0020 (8) | 0.0073 (7) | 0.0001 (8) |
C13 | 0.0188 (9) | 0.0162 (9) | 0.0285 (10) | 0.0000 (7) | 0.0002 (7) | 0.0002 (7) |
C14 | 0.0218 (9) | 0.0176 (9) | 0.0204 (9) | −0.0005 (7) | −0.0011 (7) | 0.0007 (7) |
C15 | 0.0215 (9) | 0.0152 (9) | 0.0217 (9) | −0.0008 (7) | 0.0035 (7) | −0.0008 (7) |
C16 | 0.0172 (8) | 0.0244 (10) | 0.0201 (9) | 0.0018 (7) | −0.0005 (7) | 0.0029 (7) |
C17 | 0.0168 (9) | 0.0264 (10) | 0.0317 (10) | 0.0001 (8) | −0.0008 (7) | 0.0031 (8) |
C18 | 0.0231 (11) | 0.0300 (12) | 0.0727 (17) | 0.0050 (9) | 0.0026 (11) | −0.0037 (11) |
C19 | 0.0223 (10) | 0.0320 (12) | 0.0444 (13) | −0.0052 (9) | −0.0001 (9) | −0.0004 (10) |
C20 | 0.0257 (10) | 0.0326 (11) | 0.0250 (10) | 0.0059 (8) | 0.0030 (8) | −0.0014 (8) |
C21 | 0.0255 (10) | 0.0341 (12) | 0.0247 (10) | −0.0019 (8) | 0.0012 (8) | 0.0091 (8) |
O1—C2 | 1.364 (2) | C13—C14 | 1.397 (3) |
O1—C9 | 1.458 (2) | C13—C17 | 1.520 (2) |
O2—C2 | 1.201 (2) | C14—C15 | 1.384 (2) |
C2—C3 | 1.468 (3) | C14—H14 | 0.9500 |
C3—C8 | 1.385 (3) | C15—C16 | 1.531 (2) |
C3—C4 | 1.394 (3) | C16—C21 | 1.521 (3) |
C4—C5 | 1.379 (3) | C16—C20 | 1.527 (3) |
C4—H4 | 0.9500 | C17—C18 | 1.521 (3) |
C5—C6 | 1.391 (3) | C17—C19 | 1.526 (3) |
C5—H5 | 0.9500 | C17—H17 | 1.0000 |
C6—C7 | 1.388 (3) | C18—H18A | 0.9800 |
C6—H6 | 0.9500 | C18—H18B | 0.9800 |
C7—C8 | 1.383 (3) | C18—H18C | 0.9800 |
C7—H7 | 0.9500 | C19—H19A | 0.9800 |
C8—C9 | 1.503 (3) | C19—H19B | 0.9800 |
C9—C10 | 1.514 (2) | C19—H19C | 0.9800 |
C9—C16 | 1.615 (2) | C20—H20A | 0.9800 |
C10—C15 | 1.379 (3) | C20—H20B | 0.9800 |
C10—C11 | 1.386 (3) | C20—H20C | 0.9800 |
C11—C12 | 1.388 (3) | C21—H21A | 0.9800 |
C11—H11 | 0.9500 | C21—H21B | 0.9800 |
C12—C13 | 1.405 (3) | C21—H21C | 0.9800 |
C12—H12 | 0.9500 | ||
C2—O1—C9 | 111.20 (14) | C15—C14—H14 | 121.6 |
O2—C2—O1 | 121.36 (18) | C13—C14—H14 | 121.6 |
O2—C2—C3 | 130.61 (18) | C10—C15—C14 | 122.43 (17) |
O1—C2—C3 | 108.01 (15) | C10—C15—C16 | 94.58 (15) |
C8—C3—C4 | 122.37 (19) | C14—C15—C16 | 142.93 (17) |
C8—C3—C2 | 108.38 (16) | C21—C16—C20 | 111.26 (16) |
C4—C3—C2 | 129.20 (18) | C21—C16—C15 | 117.61 (16) |
C5—C4—C3 | 117.01 (19) | C20—C16—C15 | 112.52 (15) |
C5—C4—H4 | 121.5 | C21—C16—C9 | 115.56 (15) |
C3—C4—H4 | 121.5 | C20—C16—C9 | 112.79 (15) |
C4—C5—C6 | 121.00 (19) | C15—C16—C9 | 84.77 (13) |
C4—C5—H5 | 119.5 | C13—C17—C18 | 111.91 (17) |
C6—C5—H5 | 119.5 | C13—C17—C19 | 111.17 (16) |
C7—C6—C5 | 121.6 (2) | C18—C17—C19 | 110.09 (17) |
C7—C6—H6 | 119.2 | C13—C17—H17 | 107.8 |
C5—C6—H6 | 119.2 | C18—C17—H17 | 107.8 |
C8—C7—C6 | 117.80 (18) | C19—C17—H17 | 107.8 |
C8—C7—H7 | 121.1 | C17—C18—H18A | 109.5 |
C6—C7—H7 | 121.1 | C17—C18—H18B | 109.5 |
C7—C8—C3 | 120.23 (17) | H18A—C18—H18B | 109.5 |
C7—C8—C9 | 131.08 (17) | C17—C18—H18C | 109.5 |
C3—C8—C9 | 108.65 (16) | H18A—C18—H18C | 109.5 |
O1—C9—C8 | 103.58 (14) | H18B—C18—H18C | 109.5 |
O1—C9—C10 | 114.44 (14) | C17—C19—H19A | 109.5 |
C8—C9—C10 | 119.64 (15) | C17—C19—H19B | 109.5 |
O1—C9—C16 | 112.54 (14) | H19A—C19—H19B | 109.5 |
C8—C9—C16 | 120.43 (15) | C17—C19—H19C | 109.5 |
C10—C9—C16 | 86.29 (13) | H19A—C19—H19C | 109.5 |
C15—C10—C11 | 122.18 (17) | H19B—C19—H19C | 109.5 |
C15—C10—C9 | 94.23 (15) | C16—C20—H20A | 109.5 |
C11—C10—C9 | 143.57 (17) | C16—C20—H20B | 109.5 |
C10—C11—C12 | 115.65 (17) | H20A—C20—H20B | 109.5 |
C10—C11—H11 | 122.2 | C16—C20—H20C | 109.5 |
C12—C11—H11 | 122.2 | H20A—C20—H20C | 109.5 |
C11—C12—C13 | 122.97 (17) | H20B—C20—H20C | 109.5 |
C11—C12—H12 | 118.5 | C16—C21—H21A | 109.5 |
C13—C12—H12 | 118.5 | C16—C21—H21B | 109.5 |
C14—C13—C12 | 119.97 (17) | H21A—C21—H21B | 109.5 |
C14—C13—C17 | 120.58 (17) | C16—C21—H21C | 109.5 |
C12—C13—C17 | 119.43 (17) | H21A—C21—H21C | 109.5 |
C15—C14—C13 | 116.78 (16) | H21B—C21—H21C | 109.5 |
C9—O1—C2—O2 | 177.21 (16) | C15—C10—C11—C12 | −1.1 (3) |
C9—O1—C2—C3 | −3.88 (19) | C9—C10—C11—C12 | −178.9 (2) |
O2—C2—C3—C8 | −179.56 (19) | C10—C11—C12—C13 | 0.0 (3) |
O1—C2—C3—C8 | 1.7 (2) | C11—C12—C13—C14 | 1.4 (3) |
O2—C2—C3—C4 | 3.2 (3) | C11—C12—C13—C17 | −177.22 (18) |
O1—C2—C3—C4 | −175.60 (18) | C12—C13—C14—C15 | −1.7 (3) |
C8—C3—C4—C5 | −0.2 (3) | C17—C13—C14—C15 | 176.91 (17) |
C2—C3—C4—C5 | 176.74 (18) | C11—C10—C15—C14 | 0.8 (3) |
C3—C4—C5—C6 | 0.0 (3) | C9—C10—C15—C14 | 179.43 (17) |
C4—C5—C6—C7 | −0.3 (3) | C11—C10—C15—C16 | 178.51 (18) |
C5—C6—C7—C8 | 0.7 (3) | C9—C10—C15—C16 | −2.81 (15) |
C6—C7—C8—C3 | −0.9 (3) | C13—C14—C15—C10 | 0.7 (3) |
C6—C7—C8—C9 | −178.31 (18) | C13—C14—C15—C16 | −175.6 (2) |
C4—C3—C8—C7 | 0.6 (3) | C10—C15—C16—C21 | 118.81 (17) |
C2—C3—C8—C7 | −176.85 (16) | C14—C15—C16—C21 | −64.3 (3) |
C4—C3—C8—C9 | 178.60 (16) | C10—C15—C16—C20 | −109.90 (17) |
C2—C3—C8—C9 | 1.11 (19) | C14—C15—C16—C20 | 67.0 (3) |
C2—O1—C9—C8 | 4.40 (18) | C10—C15—C16—C9 | 2.64 (14) |
C2—O1—C9—C10 | 136.35 (15) | C14—C15—C16—C9 | 179.5 (3) |
C2—O1—C9—C16 | −127.24 (15) | O1—C9—C16—C21 | 124.47 (17) |
C7—C8—C9—O1 | 174.41 (18) | C8—C9—C16—C21 | 1.9 (2) |
C3—C8—C9—O1 | −3.25 (18) | C10—C9—C16—C21 | −120.57 (17) |
C7—C8—C9—C10 | 45.6 (3) | O1—C9—C16—C20 | −5.1 (2) |
C3—C8—C9—C10 | −132.08 (17) | C8—C9—C16—C20 | −127.69 (18) |
C7—C8—C9—C16 | −58.8 (3) | C10—C9—C16—C20 | 109.86 (16) |
C3—C8—C9—C16 | 123.56 (17) | O1—C9—C16—C15 | −117.36 (15) |
O1—C9—C10—C15 | 115.77 (16) | C8—C9—C16—C15 | 120.06 (17) |
C8—C9—C10—C15 | −120.51 (17) | C10—C9—C16—C15 | −2.40 (13) |
C16—C9—C10—C15 | 2.66 (14) | C14—C13—C17—C18 | 119.9 (2) |
O1—C9—C10—C11 | −66.1 (3) | C12—C13—C17—C18 | −61.4 (2) |
C8—C9—C10—C11 | 57.6 (3) | C14—C13—C17—C19 | −116.5 (2) |
C16—C9—C10—C11 | −179.2 (3) | C12—C13—C17—C19 | 62.1 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···O2i | 0.95 | 2.45 | 3.375 (2) | 164 |
C12—H12···O2ii | 0.95 | 2.46 | 3.372 (2) | 160 |
Symmetry codes: (i) −x, −y+1, −z; (ii) −x+1, −y+1, −z. |