Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003371/qa0246sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003371/qa0246Isup2.hkl |
CCDC reference: 144700
The title optically active compound was prepared by the authors in a synthetic study on bryostatins (Ohmori et al., 2000). The angle of rotation [α]D21 is +20.9 ° (c 1.0, CHCl3). Crystals were grown from a hexane/ethyl acetate solution.
X-ray intensities were measured for -h+k+l (θ < 75°), +h+k-l (θ < 30°) and +h-k-l (θ < 30°). There were 163 Friedel pairs, which were not averaged. The completeness of symmetry unique reflections (θ < 75°) was 93.3%, which was due to the blind region of the low-temperature apparatus. The hydroxyl H atom was located from a difference synthesis. Their positional parameters were refined with restraint of O—H = 0.98 Å (s.u. 0.01 Å) with Uiso(H) = 1.2Ueq(parent atom). The other H-atom positional parameters were calculated geometrically and fixed with Uiso(H) = 1.2Ueq(parent atom). The absolute structure was determined based on a Flack parameter value of 0.03 (3).
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.
C18H24O3S | Dx = 1.208 Mg m−3 |
Mr = 320.45 | Cu Kα radiation, λ = 1.54184 Å |
Orthorhombic, P212121 | Cell parameters from 25 reflections |
a = 8.760 (2) Å | θ = 29.1–30.0° |
b = 32.090 (2) Å | µ = 1.71 mm−1 |
c = 6.269 (2) Å | T = 248 K |
V = 1762.3 (6) Å3 | Prism, colourless |
Z = 4 | 0.5 × 0.5 × 0.3 mm |
Rigaku AFC-7R diffractometer | Rint = 0.036 |
θ–2θ scans | θmax = 75°, θmin = 2.5° |
Absorption correction: integration (Coppens et al., 1965) | h = −11→5 |
Tmin = 0.476, Tmax = 0.636 | k = −20→40 |
2633 measured reflections | l = −4→8 |
2147 independent reflections | 3 standard reflections every 150 reflections |
2055 reflections with I > 2σ(I) | intensity decay: none |
Refinement on F2 | (Δ/σ)max = 0.001 |
R[F2 > 2σ(F2)] = 0.040 | Δρmax = 0.43 e Å−3 |
wR(F2) = 0.108 | Δρmin = −0.41 e Å−3 |
S = 1.08 | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
2147 reflections | Extinction coefficient: 0.0101 (6) |
203 parameters | Absolute structure: Flack (1983), 163 Friedel pairs |
H atoms treated by a mixture of independent and constrained refinement | Absolute structure parameter: 0.03 (3) |
w = 1/[σ2(Fo2) + (0.0524P)2 + 0.8338P] where P = (Fo2 + 2Fc2)/3 |
C18H24O3S | V = 1762.3 (6) Å3 |
Mr = 320.45 | Z = 4 |
Orthorhombic, P212121 | Cu Kα radiation |
a = 8.760 (2) Å | µ = 1.71 mm−1 |
b = 32.090 (2) Å | T = 248 K |
c = 6.269 (2) Å | 0.5 × 0.5 × 0.3 mm |
Rigaku AFC-7R diffractometer | 2055 reflections with I > 2σ(I) |
Absorption correction: integration (Coppens et al., 1965) | Rint = 0.036 |
Tmin = 0.476, Tmax = 0.636 | 3 standard reflections every 150 reflections |
2633 measured reflections | intensity decay: none |
2147 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.108 | Δρmax = 0.43 e Å−3 |
S = 1.08 | Δρmin = −0.41 e Å−3 |
2147 reflections | Absolute structure: Flack (1983), 163 Friedel pairs |
203 parameters | Absolute structure parameter: 0.03 (3) |
Refinement. Refinement was based on F2 against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F2, and conventional R-factor (R) was calculated on F, with F set to zero for negative F2. The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt). |
x | y | z | Uiso*/Ueq | ||
S1 | 0.8731 (1) | 0.04241 (2) | 0.2786 (2) | 0.0772 (4) | |
O2 | 1.0693 (2) | 0.13357 (5) | 0.5234 (3) | 0.0405 (5) | |
O3 | 1.0371 (2) | 0.20060 (6) | 0.4179 (4) | 0.0551 (6) | |
O4 | 0.6503 (3) | 0.22811 (8) | −0.2094 (4) | 0.0821 (9) | |
C5 | 0.9962 (3) | −0.00085 (8) | 0.2971 (5) | 0.0459 (7) | |
C6 | 1.0057 (4) | −0.02559 (8) | 0.4764 (5) | 0.0478 (7) | |
C7 | 1.1053 (4) | −0.05906 (9) | 0.4797 (6) | 0.0590 (8) | |
C8 | 1.1930 (4) | −0.0689 (1) | 0.3089 (8) | 0.068 (1) | |
C9 | 1.1843 (4) | −0.0458 (1) | 0.1305 (7) | 0.070 (1) | |
C10 | 1.0870 (4) | −0.0110 (1) | 0.1197 (5) | 0.0644 (10) | |
C11 | 0.8674 (3) | 0.06189 (8) | 0.5500 (5) | 0.0457 (7) | |
C12 | 0.8121 (3) | 0.10762 (8) | 0.5656 (5) | 0.0435 (7) | |
C13 | 0.8125 (5) | 0.1189 (1) | 0.8022 (6) | 0.066 (1) | |
C14 | 0.6509 (3) | 0.1115 (1) | 0.4714 (8) | 0.071 (1) | |
C15 | 0.9186 (3) | 0.13582 (7) | 0.4367 (4) | 0.0341 (6) | |
C16 | 0.8875 (3) | 0.18303 (7) | 0.4454 (4) | 0.0363 (6) | |
C17 | 0.7843 (3) | 0.19858 (7) | 0.2797 (5) | 0.0403 (6) | |
C18 | 0.6966 (3) | 0.21124 (8) | 0.1505 (5) | 0.0466 (7) | |
C19 | 0.5863 (4) | 0.2263 (1) | −0.0074 (6) | 0.0649 (10) | |
C20 | 1.1503 (3) | 0.16902 (8) | 0.4481 (5) | 0.0421 (6) | |
C21 | 1.2616 (4) | 0.1831 (1) | 0.6144 (7) | 0.075 (1) | |
C22 | 1.2271 (5) | 0.1602 (1) | 0.2395 (8) | 0.090 (1) | |
H4 | 0.596 (4) | 0.2495 (10) | −0.290 (6) | 0.0984* | |
H6 | 0.9414 | −0.0193 | 0.6003 | 0.0519* | |
H7 | 1.1147 | −0.0762 | 0.6067 | 0.0721* | |
H8 | 1.2589 | −0.0929 | 0.3196 | 0.0824* | |
H9 | 1.2479 | −0.0526 | 0.0061 | 0.0800* | |
H10 | 1.0848 | 0.0060 | −0.0054 | 0.0766* | |
H11A | 0.7982 | 0.0451 | 0.6332 | 0.0492* | |
H11B | 0.9677 | 0.0602 | 0.6125 | 0.0492* | |
H13A | 0.7494 | 0.1008 | 0.8826 | 0.0780* | |
H13B | 0.9187 | 0.1159 | 0.8596 | 0.0780* | |
H13C | 0.7841 | 0.1474 | 0.8240 | 0.0780* | |
H14A | 0.5807 | 0.0938 | 0.5390 | 0.0793* | |
H14B | 0.6544 | 0.1023 | 0.3154 | 0.0793* | |
H14C | 0.6170 | 0.1396 | 0.4684 | 0.0793* | |
H15 | 0.9192 | 0.1267 | 0.2900 | 0.0398* | |
H16 | 0.8450 | 0.1905 | 0.5846 | 0.0407* | |
H19A | 0.4973 | 0.2096 | 0.0001 | 0.0819* | |
H19B | 0.5577 | 0.2549 | 0.0391 | 0.0819* | |
H21A | 1.2119 | 0.1897 | 0.7458 | 0.0775* | |
H21B | 1.3407 | 0.1635 | 0.6354 | 0.0775* | |
H21C | 1.3105 | 0.2096 | 0.5637 | 0.0775* | |
H22A | 1.1577 | 0.1513 | 0.1331 | 0.1127* | |
H22B | 1.3042 | 0.1383 | 0.2604 | 0.1127* | |
H22C | 1.2812 | 0.1848 | 0.1910 | 0.1127* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.1237 (9) | 0.0398 (4) | 0.0681 (6) | 0.0140 (5) | −0.0458 (6) | −0.0045 (4) |
O2 | 0.0351 (9) | 0.0347 (8) | 0.052 (1) | 0.0014 (7) | −0.0054 (10) | 0.0086 (8) |
O3 | 0.043 (1) | 0.0367 (9) | 0.086 (2) | −0.0053 (8) | −0.006 (1) | 0.021 (1) |
O4 | 0.100 (2) | 0.085 (2) | 0.061 (1) | 0.048 (2) | 0.008 (2) | 0.032 (1) |
C5 | 0.051 (2) | 0.038 (1) | 0.049 (2) | −0.014 (1) | −0.003 (2) | −0.003 (1) |
C6 | 0.054 (2) | 0.037 (1) | 0.053 (2) | 0.002 (1) | 0.008 (2) | 0.002 (1) |
C7 | 0.058 (2) | 0.044 (1) | 0.075 (2) | 0.008 (1) | 0.002 (2) | −0.002 (2) |
C8 | 0.050 (2) | 0.067 (2) | 0.088 (3) | 0.001 (2) | 0.000 (2) | −0.025 (2) |
C9 | 0.044 (2) | 0.086 (2) | 0.080 (3) | −0.015 (2) | 0.019 (2) | −0.038 (2) |
C10 | 0.075 (2) | 0.071 (2) | 0.047 (2) | −0.040 (2) | −0.002 (2) | 0.000 (2) |
C11 | 0.049 (2) | 0.031 (1) | 0.056 (2) | −0.002 (1) | −0.004 (2) | 0.010 (1) |
C12 | 0.039 (1) | 0.032 (1) | 0.059 (2) | 0.001 (1) | 0.005 (1) | 0.012 (1) |
C13 | 0.090 (3) | 0.047 (2) | 0.060 (2) | 0.009 (2) | 0.036 (2) | 0.013 (2) |
C14 | 0.035 (1) | 0.053 (2) | 0.126 (4) | −0.003 (1) | 0.001 (2) | 0.029 (2) |
C15 | 0.033 (1) | 0.030 (1) | 0.039 (1) | 0.0024 (10) | −0.003 (1) | 0.004 (1) |
C16 | 0.037 (1) | 0.031 (1) | 0.041 (1) | 0.001 (1) | 0.001 (1) | 0.005 (1) |
C17 | 0.042 (1) | 0.033 (1) | 0.046 (1) | 0.004 (1) | 0.001 (1) | 0.007 (1) |
C18 | 0.044 (1) | 0.043 (1) | 0.053 (2) | 0.005 (1) | 0.001 (2) | 0.010 (1) |
C19 | 0.050 (2) | 0.086 (2) | 0.059 (2) | 0.012 (2) | −0.001 (2) | 0.024 (2) |
C20 | 0.036 (1) | 0.037 (1) | 0.053 (2) | −0.003 (1) | 0.001 (1) | 0.002 (1) |
C21 | 0.070 (2) | 0.055 (2) | 0.100 (3) | −0.009 (2) | −0.035 (2) | 0.003 (2) |
C22 | 0.093 (3) | 0.075 (2) | 0.101 (3) | −0.021 (2) | 0.051 (3) | −0.012 (2) |
S1—C5 | 1.762 (3) | C12—C15 | 1.531 (4) |
S1—C11 | 1.813 (3) | C13—H13A | 0.95 |
O2—C15 | 1.429 (3) | C13—H13B | 1.00 |
O2—C20 | 1.422 (3) | C13—H13C | 0.96 |
O3—C16 | 1.437 (3) | C14—H14A | 0.94 |
O3—C20 | 1.431 (3) | C14—H14B | 1.02 |
O4—C19 | 1.386 (4) | C14—H14C | 0.95 |
O4—H4 | 0.98 (3) | C15—C16 | 1.540 (3) |
C5—C6 | 1.378 (4) | C15—H15 | 0.97 |
C5—C10 | 1.405 (5) | C16—C17 | 1.465 (4) |
C6—C7 | 1.384 (4) | C16—H16 | 0.98 |
C6—H6 | 0.98 | C17—C18 | 1.188 (4) |
C7—C8 | 1.355 (6) | C18—C19 | 1.465 (5) |
C7—H7 | 0.97 | C19—H19A | 0.95 |
C8—C9 | 1.344 (6) | C19—H19B | 1.00 |
C8—H8 | 0.97 | C20—C21 | 1.497 (5) |
C9—C10 | 1.406 (5) | C20—C22 | 1.498 (6) |
C9—H9 | 0.98 | C21—H21A | 0.96 |
C10—H10 | 0.96 | C21—H21B | 0.95 |
C11—C12 | 1.548 (4) | C21—H21C | 1.00 |
C11—H11A | 0.96 | C22—H22A | 0.95 |
C11—H11B | 0.96 | C22—H22B | 0.98 |
C12—C13 | 1.527 (5) | C22—H22C | 0.97 |
C12—C14 | 1.536 (4) | ||
C5—S1—C11 | 103.1 (1) | C12—C14—H14C | 112 |
C15—O2—C20 | 107.1 (2) | H14A—C14—H14B | 106 |
C16—O3—C20 | 109.8 (2) | H14A—C14—H14C | 112 |
C19—O4—H4 | 107 (2) | H14B—C14—H14C | 105 |
S1—C5—C6 | 123.0 (2) | O2—C15—C12 | 109.4 (2) |
S1—C5—C10 | 118.5 (2) | O2—C15—C16 | 101.5 (2) |
C6—C5—C10 | 118.5 (3) | O2—C15—H15 | 110 |
C5—C6—C7 | 119.8 (3) | C12—C15—C16 | 117.1 (2) |
C5—C6—H6 | 120 | C12—C15—H15 | 109 |
C7—C6—H6 | 121 | C16—C15—H15 | 109 |
C6—C7—C8 | 121.7 (3) | O3—C16—C15 | 102.7 (2) |
C6—C7—H7 | 120 | O3—C16—C17 | 110.1 (2) |
C8—C7—H7 | 118 | O3—C16—H16 | 111 |
C7—C8—C9 | 119.9 (3) | C15—C16—C17 | 114.8 (2) |
C7—C8—H8 | 118 | C15—C16—H16 | 110 |
C9—C8—H8 | 122 | C17—C16—H16 | 108 |
C8—C9—C10 | 120.8 (4) | C16—C17—C18 | 177.7 (3) |
C8—C9—H9 | 120 | C17—C18—C19 | 178.9 (3) |
C10—C9—H9 | 119 | O4—C19—C18 | 111.4 (3) |
C5—C10—C9 | 119.3 (3) | O4—C19—H19A | 114 |
C5—C10—H10 | 120 | O4—C19—H19B | 109 |
C9—C10—H10 | 120 | C18—C19—H19A | 109 |
S1—C11—C12 | 113.3 (2) | C18—C19—H19B | 106 |
S1—C11—H11A | 110 | H19A—C19—H19B | 108 |
S1—C11—H11B | 110 | O2—C20—O3 | 105.3 (2) |
C12—C11—H11A | 107 | O2—C20—C21 | 109.6 (3) |
C12—C11—H11B | 108 | O2—C20—C22 | 111.2 (2) |
H11A—C11—H11B | 109 | O3—C20—C21 | 109.2 (2) |
C11—C12—C13 | 106.6 (2) | O3—C20—C22 | 109.3 (3) |
C11—C12—C14 | 109.9 (2) | C21—C20—C22 | 111.9 (3) |
C11—C12—C15 | 109.6 (2) | C20—C21—H21A | 111 |
C13—C12—C14 | 110.9 (3) | C20—C21—H21B | 112 |
C13—C12—C15 | 111.8 (2) | C20—C21—H21C | 108 |
C14—C12—C15 | 108.0 (3) | H21A—C21—H21B | 111 |
C12—C13—H13A | 112 | H21A—C21—H21C | 106 |
C12—C13—H13B | 109 | H21B—C21—H21C | 107 |
C12—C13—H13C | 111 | C20—C22—H22A | 113 |
H13A—C13—H13B | 107 | C20—C22—H22B | 109 |
H13A—C13—H13C | 111 | C20—C22—H22C | 110 |
H13B—C13—H13C | 106 | H22A—C22—H22B | 109 |
C12—C14—H14A | 112 | H22A—C22—H22C | 110 |
C12—C14—H14B | 109 | H22B—C22—H22C | 107 |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.98 (3) | 1.86 (3) | 2.816 (3) | 164 (3) |
Symmetry code: (i) x−1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C18H24O3S |
Mr | 320.45 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 248 |
a, b, c (Å) | 8.760 (2), 32.090 (2), 6.269 (2) |
V (Å3) | 1762.3 (6) |
Z | 4 |
Radiation type | Cu Kα |
µ (mm−1) | 1.71 |
Crystal size (mm) | 0.5 × 0.5 × 0.3 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | Integration (Coppens et al., 1965) |
Tmin, Tmax | 0.476, 0.636 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2633, 2147, 2055 |
Rint | 0.036 |
(sin θ/λ)max (Å−1) | 0.626 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.108, 1.08 |
No. of reflections | 2147 |
No. of parameters | 203 |
No. of restraints | ? |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.43, −0.41 |
Absolute structure | Flack (1983), 163 Friedel pairs |
Absolute structure parameter | 0.03 (3) |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993), MSC/AFC Diffractometer Control Software, TEXSAN (Molecular Structure Corporation, 1999), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), TEXSAN.
S1—C5 | 1.762 (3) | C17—C18 | 1.188 (4) |
S1—C11 | 1.813 (3) | C18—C19 | 1.465 (5) |
C16—C17 | 1.465 (4) | ||
C5—S1—C11 | 103.1 (1) | C17—C18—C19 | 178.9 (3) |
C16—C17—C18 | 177.7 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O4—H4···O3i | 0.98 (3) | 1.86 (3) | 2.816 (3) | 164 (3) |
Symmetry code: (i) x−1/2, −y+1/2, −z. |
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A synthetic study on bryostatin 3 has been reported (Obitsu et al., 1998).