Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100013147/fr1303sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270100013147/fr1303Isup2.hkl |
CCDC reference: 156185
Compound (I) was prepared as described previously by Cuthbertson et al. (1975) and was recrystallized from ethanol, giving colourless needles [m.p. 455–458 K (decomp.)].
H atoms were placed geometrically with C—H = 0.95 Å (0.98 Å for methyl H) and refined with a riding model (including free rotation about C—C bonds for methyl groups), with Uiso constrained to be 1.2 (1.5 for methyl groups) times Ueq of the carrier atom.
Data collection: SMART (Bruker, 1997); cell refinement: SMART and SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 1997); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
C20H22O3S | F(000) = 364 |
Mr = 342.44 | Dx = 1.330 Mg m−3 |
Triclinic, P1 | Melting point = 455–458 K |
a = 6.0507 (5) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.6570 (9) Å | Cell parameters from 5133 reflections |
c = 15.4541 (14) Å | θ = 2.2–29.1° |
α = 82.093 (8)° | µ = 0.20 mm−1 |
β = 78.738 (6)° | T = 123 K |
γ = 75.898 (5)° | Prism, colourless |
V = 855.08 (13) Å3 | 0.40 × 0.25 × 0.20 mm |
Z = 2 |
Bruker 1K CCD area-detector diffractometer | 2844 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.015 |
Graphite monochromator | θmax = 26.4°, θmin = 2.2° |
Detector resolution: 8.192 pixels mm-1 | h = −7→7 |
narrow frame ω scans | k = −12→12 |
7324 measured reflections | l = −18→19 |
3459 independent reflections |
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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.02 | w = 1/[σ2(Fo2) + (0.07P)2] where P = (Fo2 + 2Fc2)/3 |
3459 reflections | (Δ/σ)max < 0.001 |
221 parameters | Δρmax = 0.31 e Å−3 |
0 restraints | Δρmin = −0.26 e Å−3 |
C20H22O3S | γ = 75.898 (5)° |
Mr = 342.44 | V = 855.08 (13) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.0507 (5) Å | Mo Kα radiation |
b = 9.6570 (9) Å | µ = 0.20 mm−1 |
c = 15.4541 (14) Å | T = 123 K |
α = 82.093 (8)° | 0.40 × 0.25 × 0.20 mm |
β = 78.738 (6)° |
Bruker 1K CCD area-detector diffractometer | 2844 reflections with I > 2σ(I) |
7324 measured reflections | Rint = 0.015 |
3459 independent reflections |
R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
wR(F2) = 0.097 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.31 e Å−3 |
3459 reflections | Δρmin = −0.26 e Å−3 |
221 parameters |
Experimental. The data collection nominally covered a sphere of reciprocal space by a combination of three sets of exposures; each set had a different ϕ angle for the crystal, 0, 120 and 240°, repectively. Each exposure covered 0.3° in ω with a 30 s correlated frame time. A total of 600 frames were accumalated in each ω sweep. The crystal to detector distance was 4.935 cm. Coverage of the unique set was 87.2% to 29.13° in θ (0.73 Å) and 98.8% complete to 26.37° in θ (0.80 Å). Crystal decay was monitored by repeating the initial 50 frames at the end of data collection and analyzing the duplicate reflections; a further 50 frames of data were collected at positive 2θ to improve cell refinement statistics. The data were truncated to 0.80 Å for structure refinement. Area detector scaling and absorption corrections were performed by SADABS (Bruker, 1997). This correction was used to scale the frames of data and to correct for absorption of the primary beam by the crystal support using the method of Blessing (1995). A correction for absorption of the primary beam by the crystal was not applied and as such no transmission factors are quoted. |
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 | ||
S1 | 0.18724 (6) | 0.36650 (4) | 0.30752 (2) | 0.02190 (12) | |
O1 | 0.13998 (16) | 0.17180 (10) | 0.17777 (6) | 0.0220 (2) | |
O2 | 0.13827 (15) | 0.08330 (10) | 0.26333 (6) | 0.0203 (2) | |
O3 | 0.50154 (15) | 0.11321 (10) | 0.21065 (6) | 0.0178 (2) | |
C1 | 0.4563 (2) | 0.20528 (14) | 0.06263 (9) | 0.0202 (3) | |
C2 | 0.3107 (3) | 0.23670 (16) | −0.00094 (10) | 0.0258 (3) | |
H2A | 0.1485 | 0.2687 | 0.0165 | 0.031* | |
C3 | 0.4030 (3) | 0.22118 (16) | −0.08905 (10) | 0.0299 (4) | |
H3A | 0.3035 | 0.2421 | −0.1319 | 0.036* | |
C4 | 0.6387 (3) | 0.17550 (16) | −0.11550 (10) | 0.0294 (4) | |
H4A | 0.7008 | 0.1645 | −0.1762 | 0.035* | |
C5 | 0.7845 (3) | 0.14577 (16) | −0.05266 (10) | 0.0277 (3) | |
H5A | 0.9467 | 0.1150 | −0.0705 | 0.033* | |
C6 | 0.6935 (2) | 0.16094 (15) | 0.03564 (9) | 0.0232 (3) | |
H6A | 0.7937 | 0.1409 | 0.0782 | 0.028* | |
C7 | 0.3572 (2) | 0.21752 (14) | 0.15981 (9) | 0.0192 (3) | |
C8 | 0.3241 (2) | 0.36882 (14) | 0.19027 (9) | 0.0203 (3) | |
C9 | 0.1533 (3) | 0.48171 (15) | 0.14157 (10) | 0.0253 (3) | |
H9A | 0.2223 | 0.4968 | 0.0791 | 0.038* | |
H9B | 0.1176 | 0.5722 | 0.1688 | 0.038* | |
H9C | 0.0107 | 0.4483 | 0.1457 | 0.038* | |
C10 | 0.5572 (2) | 0.41249 (15) | 0.17563 (10) | 0.0239 (3) | |
H10A | 0.6120 | 0.4295 | 0.1119 | 0.036* | |
H10B | 0.6703 | 0.3355 | 0.2017 | 0.036* | |
H10C | 0.5383 | 0.5004 | 0.2039 | 0.036* | |
C11 | 0.3240 (2) | 0.19025 (14) | 0.35739 (9) | 0.0196 (3) | |
C12 | 0.5561 (2) | 0.19121 (16) | 0.38289 (10) | 0.0248 (3) | |
H12A | 0.6149 | 0.0991 | 0.4152 | 0.037* | |
H12B | 0.5346 | 0.2687 | 0.4206 | 0.037* | |
H12C | 0.6673 | 0.2064 | 0.3291 | 0.037* | |
C13 | 0.1521 (2) | 0.16152 (16) | 0.44105 (9) | 0.0246 (3) | |
H13A | 0.2177 | 0.0714 | 0.4738 | 0.037* | |
H13B | 0.0075 | 0.1544 | 0.4243 | 0.037* | |
H13C | 0.1213 | 0.2404 | 0.4785 | 0.037* | |
C14 | 0.3570 (2) | 0.07823 (14) | 0.29035 (9) | 0.0179 (3) | |
C15 | 0.4540 (2) | −0.07564 (14) | 0.32400 (8) | 0.0186 (3) | |
C16 | 0.3067 (2) | −0.16325 (15) | 0.36784 (9) | 0.0216 (3) | |
H16A | 0.1449 | −0.1248 | 0.3803 | 0.026* | |
C17 | 0.3953 (3) | −0.30634 (16) | 0.39332 (10) | 0.0267 (3) | |
H17A | 0.2938 | −0.3657 | 0.4226 | 0.032* | |
C18 | 0.6315 (3) | −0.36314 (16) | 0.37616 (10) | 0.0272 (3) | |
H18A | 0.6919 | −0.4613 | 0.3933 | 0.033* | |
C19 | 0.7794 (3) | −0.27569 (16) | 0.33375 (10) | 0.0257 (3) | |
H19A | 0.9415 | −0.3140 | 0.3226 | 0.031* | |
C20 | 0.6915 (2) | −0.13251 (15) | 0.30757 (9) | 0.0218 (3) | |
H20A | 0.7934 | −0.0733 | 0.2784 | 0.026* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0225 (2) | 0.01777 (19) | 0.0229 (2) | −0.00087 (13) | −0.00198 (14) | −0.00263 (13) |
O1 | 0.0207 (5) | 0.0250 (5) | 0.0215 (5) | −0.0090 (4) | −0.0080 (4) | 0.0076 (4) |
O2 | 0.0182 (5) | 0.0243 (5) | 0.0185 (5) | −0.0068 (4) | −0.0055 (4) | 0.0047 (4) |
O3 | 0.0161 (5) | 0.0187 (5) | 0.0174 (5) | −0.0028 (4) | −0.0037 (4) | 0.0016 (4) |
C1 | 0.0249 (7) | 0.0150 (7) | 0.0212 (7) | −0.0058 (5) | −0.0054 (6) | 0.0013 (5) |
C2 | 0.0277 (8) | 0.0251 (8) | 0.0267 (8) | −0.0082 (6) | −0.0097 (6) | 0.0015 (6) |
C3 | 0.0433 (10) | 0.0273 (8) | 0.0242 (8) | −0.0142 (7) | −0.0135 (7) | 0.0033 (6) |
C4 | 0.0473 (10) | 0.0221 (8) | 0.0203 (7) | −0.0133 (7) | −0.0029 (7) | −0.0015 (6) |
C5 | 0.0324 (8) | 0.0206 (8) | 0.0271 (8) | −0.0045 (6) | −0.0001 (6) | −0.0014 (6) |
C6 | 0.0268 (8) | 0.0205 (7) | 0.0211 (7) | −0.0045 (6) | −0.0047 (6) | 0.0012 (6) |
C7 | 0.0168 (7) | 0.0190 (7) | 0.0221 (7) | −0.0042 (5) | −0.0061 (5) | 0.0018 (5) |
C8 | 0.0199 (7) | 0.0190 (7) | 0.0212 (7) | −0.0039 (5) | −0.0040 (5) | 0.0007 (5) |
C9 | 0.0237 (7) | 0.0204 (7) | 0.0300 (8) | −0.0032 (6) | −0.0061 (6) | 0.0026 (6) |
C10 | 0.0238 (8) | 0.0212 (7) | 0.0277 (8) | −0.0084 (6) | −0.0037 (6) | −0.0007 (6) |
C11 | 0.0193 (7) | 0.0193 (7) | 0.0194 (7) | −0.0021 (5) | −0.0048 (5) | −0.0008 (5) |
C12 | 0.0262 (8) | 0.0258 (8) | 0.0248 (7) | −0.0054 (6) | −0.0089 (6) | −0.0042 (6) |
C13 | 0.0257 (8) | 0.0262 (8) | 0.0199 (7) | −0.0038 (6) | −0.0022 (6) | −0.0015 (6) |
C14 | 0.0147 (6) | 0.0208 (7) | 0.0181 (7) | −0.0043 (5) | −0.0028 (5) | −0.0007 (5) |
C15 | 0.0226 (7) | 0.0186 (7) | 0.0151 (6) | −0.0031 (5) | −0.0057 (5) | −0.0024 (5) |
C16 | 0.0219 (7) | 0.0231 (7) | 0.0190 (7) | −0.0042 (6) | −0.0033 (6) | −0.0007 (6) |
C17 | 0.0331 (8) | 0.0233 (8) | 0.0243 (8) | −0.0092 (6) | −0.0049 (6) | 0.0007 (6) |
C18 | 0.0363 (9) | 0.0185 (7) | 0.0261 (8) | −0.0012 (6) | −0.0109 (7) | −0.0006 (6) |
C19 | 0.0244 (8) | 0.0259 (8) | 0.0254 (8) | 0.0014 (6) | −0.0077 (6) | −0.0054 (6) |
C20 | 0.0212 (7) | 0.0225 (7) | 0.0218 (7) | −0.0037 (6) | −0.0051 (6) | −0.0026 (6) |
S1—C11 | 1.8378 (14) | C18—C19 | 1.390 (2) |
S1—C8 | 1.8389 (14) | C19—C20 | 1.389 (2) |
O1—C7 | 1.4509 (15) | C2—H2A | 0.9500 |
O1—O2 | 1.4721 (12) | C3—H3A | 0.9500 |
O2—C14 | 1.4517 (15) | C4—H4A | 0.9500 |
O3—C14 | 1.4158 (15) | C5—H5A | 0.9500 |
O3—C7 | 1.4202 (15) | C6—H6A | 0.9500 |
C1—C6 | 1.390 (2) | C9—H9A | 0.9800 |
C1—C2 | 1.3999 (19) | C9—H9B | 0.9800 |
C1—C7 | 1.5139 (19) | C9—H9C | 0.9800 |
C2—C3 | 1.381 (2) | C10—H10A | 0.9800 |
C3—C4 | 1.382 (2) | C10—H10B | 0.9800 |
C4—C5 | 1.392 (2) | C10—H10C | 0.9800 |
C5—C6 | 1.382 (2) | C12—H12A | 0.9800 |
C7—C8 | 1.5513 (19) | C12—H12B | 0.9800 |
C8—C9 | 1.5338 (18) | C12—H12C | 0.9800 |
C8—C10 | 1.5355 (18) | C13—H13A | 0.9800 |
C11—C12 | 1.5338 (19) | C13—H13B | 0.9800 |
C11—C13 | 1.5317 (19) | C13—H13C | 0.9800 |
C11—C14 | 1.5511 (19) | C16—H16A | 0.9500 |
C14—C15 | 1.5181 (18) | C17—H17A | 0.9500 |
C15—C16 | 1.3940 (19) | C18—H18A | 0.9500 |
C15—C20 | 1.3936 (19) | C19—H19A | 0.9500 |
C16—C17 | 1.387 (2) | C20—H20A | 0.9500 |
C17—C18 | 1.387 (2) | ||
C1···C4i | 3.813 (2) | H3A···C19i | 3.22 |
C2···C5i | 3.830 (2) | H4A···C16i | 2.97 |
C3···C6i | 3.829 (2) | ||
C11—S1—C8 | 104.21 (6) | C3—C2—H2A | 120.0 |
C7—O1—O2 | 105.75 (8) | C1—C2—H2A | 120.0 |
C14—O2—O1 | 105.96 (8) | C2—C3—H3A | 119.6 |
C14—O3—C7 | 106.04 (9) | C4—C3—H3A | 119.6 |
C6—C1—C2 | 119.21 (13) | C3—C4—H4A | 120.2 |
C6—C1—C7 | 120.23 (12) | C5—C4—H4A | 120.2 |
C2—C1—C7 | 120.55 (13) | C6—C5—H5A | 120.0 |
C3—C2—C1 | 119.91 (14) | C4—C5—H5A | 120.0 |
C2—C3—C4 | 120.70 (14) | C5—C6—H6A | 119.7 |
C3—C4—C5 | 119.60 (14) | C1—C6—H6A | 119.7 |
C6—C5—C4 | 120.05 (15) | C8—C9—H9A | 109.5 |
C5—C6—C1 | 120.51 (13) | C8—C9—H9B | 109.5 |
O3—C7—O1 | 103.96 (10) | H9A—C9—H9B | 109.5 |
O3—C7—C1 | 108.39 (11) | C8—C9—H9C | 109.5 |
O1—C7—C1 | 107.90 (10) | H9A—C9—H9C | 109.5 |
O3—C7—C8 | 110.57 (10) | H9B—C9—H9C | 109.5 |
O1—C7—C8 | 110.89 (11) | C8—C10—H10A | 109.5 |
C1—C7—C8 | 114.56 (11) | C8—C10—H10B | 109.5 |
C9—C8—C10 | 109.83 (11) | H10A—C10—H10B | 109.5 |
C9—C8—C7 | 111.65 (11) | C8—C10—H10C | 109.5 |
C10—C8—C7 | 110.38 (11) | H10A—C10—H10C | 109.5 |
C9—C8—S1 | 104.71 (10) | H10B—C10—H10C | 109.5 |
C10—C8—S1 | 111.59 (10) | C11—C12—H12A | 109.5 |
C7—C8—S1 | 108.56 (9) | C11—C12—H12B | 109.5 |
C13—C11—C12 | 109.64 (11) | H12A—C12—H12B | 109.5 |
C13—C11—C14 | 111.70 (11) | C11—C12—H12C | 109.5 |
C12—C11—C14 | 110.58 (11) | H12A—C12—H12C | 109.5 |
C13—C11—S1 | 104.48 (9) | H12B—C12—H12C | 109.5 |
C12—C11—S1 | 111.94 (9) | C11—C13—H13A | 109.5 |
C14—C11—S1 | 108.36 (9) | C11—C13—H13B | 109.5 |
O3—C14—O2 | 104.25 (10) | H13A—C13—H13B | 109.5 |
O3—C14—C15 | 108.28 (11) | C11—C13—H13C | 109.5 |
O2—C14—C15 | 107.81 (10) | H13A—C13—H13C | 109.5 |
O3—C14—C11 | 110.85 (10) | H13B—C13—H13C | 109.5 |
O2—C14—C11 | 110.08 (10) | C17—C16—H16A | 119.9 |
C15—C14—C11 | 114.99 (11) | C15—C16—H16A | 119.9 |
C16—C15—C20 | 119.36 (12) | C16—C17—H17A | 119.9 |
C16—C15—C14 | 120.57 (12) | C18—C17—H17A | 119.9 |
C20—C15—C14 | 120.00 (12) | C17—C18—H18A | 120.2 |
C17—C16—C15 | 120.28 (13) | C19—C18—H18A | 120.2 |
C16—C17—C18 | 120.28 (13) | C18—C19—H19A | 119.8 |
C17—C18—C19 | 119.65 (13) | C20—C19—H19A | 119.8 |
C18—C19—C20 | 120.31 (14) | C19—C20—H20A | 120.0 |
C19—C20—C15 | 120.10 (13) | C15—C20—H20A | 120.0 |
C7—O1—O2—C14 | −1.45 (12) | C8—S1—C11—C13 | −157.84 (9) |
C6—C1—C2—C3 | 1.1 (2) | C8—S1—C11—C12 | 83.58 (11) |
C7—C1—C2—C3 | −178.18 (13) | C8—S1—C11—C14 | −38.62 (10) |
C1—C2—C3—C4 | −0.3 (2) | C7—O3—C14—O2 | 36.19 (12) |
C2—C3—C4—C5 | −0.4 (2) | C7—O3—C14—C15 | 150.78 (10) |
C3—C4—C5—C6 | 0.5 (2) | C7—O3—C14—C11 | −82.22 (12) |
C4—C5—C6—C1 | 0.3 (2) | O1—O2—C14—O3 | −20.78 (12) |
C2—C1—C6—C5 | −1.0 (2) | O1—O2—C14—C15 | −135.71 (10) |
C7—C1—C6—C5 | 178.22 (12) | O1—O2—C14—C11 | 98.14 (11) |
C14—O3—C7—O1 | −37.10 (12) | C13—C11—C14—O3 | 175.24 (10) |
C14—O3—C7—C1 | −151.71 (10) | C12—C11—C14—O3 | −62.35 (14) |
C14—O3—C7—C8 | 81.96 (12) | S1—C11—C14—O3 | 60.68 (12) |
O2—O1—C7—O3 | 23.04 (12) | C13—C11—C14—O2 | 60.43 (14) |
O2—O1—C7—C1 | 138.00 (10) | C12—C11—C14—O2 | −177.16 (10) |
O2—O1—C7—C8 | −95.80 (11) | S1—C11—C14—O2 | −54.13 (12) |
C6—C1—C7—O3 | −30.96 (16) | C13—C11—C14—C15 | −61.54 (15) |
C2—C1—C7—O3 | 148.27 (12) | C12—C11—C14—C15 | 60.86 (14) |
C6—C1—C7—O1 | −142.96 (12) | S1—C11—C14—C15 | −176.10 (9) |
C2—C1—C7—O1 | 36.27 (16) | O3—C14—C15—C16 | −145.74 (12) |
C6—C1—C7—C8 | 93.02 (15) | O2—C14—C15—C16 | −33.50 (16) |
C2—C1—C7—C8 | −87.75 (15) | C11—C14—C15—C16 | 89.69 (15) |
O3—C7—C8—C9 | −175.41 (10) | O3—C14—C15—C20 | 31.27 (16) |
O1—C7—C8—C9 | −60.64 (14) | O2—C14—C15—C20 | 143.50 (12) |
C1—C7—C8—C9 | 61.78 (15) | C11—C14—C15—C20 | −93.30 (15) |
O3—C7—C8—C10 | 62.12 (14) | C20—C15—C16—C17 | −1.2 (2) |
O1—C7—C8—C10 | 176.89 (10) | C14—C15—C16—C17 | 175.79 (12) |
C1—C7—C8—C10 | −60.69 (15) | C15—C16—C17—C18 | 0.6 (2) |
O3—C7—C8—S1 | −60.49 (12) | C16—C17—C18—C19 | 0.4 (2) |
O1—C7—C8—S1 | 54.29 (12) | C17—C18—C19—C20 | −0.8 (2) |
C1—C7—C8—S1 | 176.70 (9) | C18—C19—C20—C15 | 0.2 (2) |
C11—S1—C8—C9 | 158.09 (9) | C16—C15—C20—C19 | 0.8 (2) |
C11—S1—C8—C10 | −83.15 (11) | C14—C15—C20—C19 | −176.22 (12) |
C11—S1—C8—C7 | 38.72 (10) |
Symmetry code: (i) −x+1, −y, −z. |
Experimental details
Crystal data | |
Chemical formula | C20H22O3S |
Mr | 342.44 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 6.0507 (5), 9.6570 (9), 15.4541 (14) |
α, β, γ (°) | 82.093 (8), 78.738 (6), 75.898 (5) |
V (Å3) | 855.08 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.20 |
Crystal size (mm) | 0.40 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker 1K CCD area-detector diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7324, 3459, 2844 |
Rint | 0.015 |
(sin θ/λ)max (Å−1) | 0.625 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.097, 1.02 |
No. of reflections | 3459 |
No. of parameters | 221 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: SMART (Bruker, 1997), SMART and SAINT (Bruker, 1997), SAINT, SHELXTL (Sheldrick, 1997), SHELXTL.
S1—C11 | 1.8378 (14) | O3—C7 | 1.4202 (15) |
S1—C8 | 1.8389 (14) | C1—C7 | 1.5139 (19) |
O1—C7 | 1.4509 (15) | C7—C8 | 1.5513 (19) |
O1—O2 | 1.4721 (12) | C11—C14 | 1.5511 (19) |
O2—C14 | 1.4517 (15) | C14—C15 | 1.5181 (18) |
O3—C14 | 1.4158 (15) | ||
C1···C4i | 3.813 (2) | H3A···C19i | 3.22 |
C2···C5i | 3.830 (2) | H4A···C16i | 2.97 |
C3···C6i | 3.829 (2) | ||
C11—S1—C8 | 104.21 (6) | O1—C7—C8 | 110.89 (11) |
C7—O1—O2 | 105.75 (8) | C7—C8—S1 | 108.56 (9) |
C14—O2—O1 | 105.96 (8) | C14—C11—S1 | 108.36 (9) |
C14—O3—C7 | 106.04 (9) | O3—C14—O2 | 104.25 (10) |
O3—C7—O1 | 103.96 (10) | O3—C14—C11 | 110.85 (10) |
O3—C7—C8 | 110.57 (10) | O2—C14—C11 | 110.08 (10) |
C7—O1—O2—C14 | −1.45 (12) | O1—O2—C14—O3 | −20.78 (12) |
O2—O1—C7—O3 | 23.04 (12) | S1—C11—C14—O3 | 60.68 (12) |
C2—C1—C7—O1 | 36.27 (16) | O2—C14—C15—C16 | −33.50 (16) |
O3—C7—C8—S1 | −60.49 (12) |
Symmetry code: (i) −x+1, −y, −z. |
Conventionally, ozonides are prepared by the action of molecular ozone, O3, on alkenes (March, 1992). We have described the facile high-yield formation of a stable ozonide, (I), by air (or neat O2) oxidation of 2,2,4,4-tetramethyl-1,5-diphenyl-8-oxa-3-thia-6,7-diazabicyclo[3.2.1]octane, (II), in benzene solution at room temperature (Cuthbertson et al., 1975). This communication gives the first structural details concerning this novel ozonide, (I), and reports the outcome of a literature survey of ozonides undertaken to establish any relationship between the O—O bond length and the endocyclic C—O—O—C torsion angle. \sch
The molecule of (I) has symmetry close to Cs, with a non-crystallographic mirror plane passing through O3 and S1 and bisecting the ozonide O—O bond, as illustrated in Fig. 1. The symmetry may also be appreciated by consideration of the following pairs of corresponding torsion angles: O1—O2—C14—O3 and O2—O1—C7—O3, −20.8 (1) and 23.0 (1)°, respectively, O3—C7—C8—S1 and O3—C14—C11—S1, −60.5 (1) and 60.7 (1)°, respectively, and O1—C7—C1—C2 and O2—C14—C15—C16, 36.3 (2) and −33.5 (2)°, respectively. Selected structural parameters, including other torsion angles, are given in Table 1. The close approach to Cs symmetry in (I) also extends to the bond lengths (Table 1) and, interestingly, the marked asymmetry often found for the C—O bonds involving the peroxy moiety of the ozonide (Tzou et al., 1996) is not present in (I), since the O1—C7 and O2—C14 bond lengths [1.4509 (15) and 1.4517 (15) Å, respectively] do not differ significantly.
The ozonide ring has an envelope conformation, with O3 displaced by −0.513 (2) Å from the mean plane of C7, O1, O2 and C14, which are coplanar (r.m.s. deviation 0.007 Å). The six-membered 1,4-oxathiane ring has a chair conformation, with C7, C8, C11 and C14 coplanar (r.m.s. deviation 0.000 Å) and S1 and O3 displaced by −0.684 (2) and 0.807 (1) Å, respectively, from this mean plane. Comparison of the angle α subtended between the planes defined by C8, S1 and C11 and C7, C8, C11 and C14 [37.27 (5)°] with the corresponding α parameter for a system unconstrained by bridging such as trans-2,3-dichloro-1,4-oxathiane (46.1°; Desseyn et al., 1972) indicates the presence of an inverse reflex effect (Jefford et al., 1970). Thus `pinching' brought about by the syn-axial placement of the O—O bridge in (I) results in a displacement of S1 towards the plane described by the four C atoms, with a corresponding decrease in the value of α. The corresponding value of α in (II), reflecting the presence of its two-atom hydrazo-bridge, is 36.2° (Cuthbertson et al., 1975).
Searching the Cambridge Structural Database (CSD; Allen & Kennard 1993) for the five-membered ozone substructure [C7, O1, O2, C14 and O3 in (I)] identifies 47 crystallographically unique fragments. The O—O bond length in (I) of 1.4721 (12) Å is indistinguishable from the average value for these 47 ozonides of 1.473 (11) Å and may be compared with the value of 1.481 (10) Å for the corresponding bond in 3,4aβ,5,7,8,8a-hexahydro-3,3-dimethyl-7β,8aβ-diphenyl-5α,7α-epidioxy- pyrano[3,4-e]-1,2,4-trioxane at 295 K (Buckleton et al., 1995), the respective C—O—O—C torsion angles being −1.45 (12) and 7.4 (8)°. The majority of the O—O bond lengths lie in the range ~1.46–1.50 Å, with a wide range of C—O—O—C torsion angles spanning 0° to ~50°.
Seeking to establish whether or not a correlation exists between the O—O bond length and the C—O—O—C torsion angle in the ozone ring, a scattergram of O—O distance versus C—O—O—C torsion angle was generated. No apparent general correlation between these two parameters was revealed, with 27 cases having a torsion angle in a narrow range of 0 to ±10° and with O—O bond lengths spanning ~1.445–1.497 Å. Interestingly, a relatively isolated group of ten cases with torsion angles in the range ±40–50° displayed a narrower range of O—O bond lengths [~ 1.465–1.475 Å], possibly reflecting a reduced range of strain energy associated with relaxation of the endocyclic C—O—O—C torsion angle.
A packing diagram for (I) is shown in Fig. 2. There are no formal hydrogen bonds present in the structure, although the packing diagram reveals both a π-π ring-stacking interaction and a C—H···π edge-to-face interaction with a centrosymmetrically related molecule; contact distances are given in Table 2.