The title compound, C
16H
22O
3S, exhibits a conformational arrangement that permits intramolecular O—H
O—S hydrogen bonds. Intermolecular bifurcated hydorgen bonding between the hydroxyl H and the sulfone O atoms, observed in the unmethylated derivative, is disrupted by the presence of the methyl group at the 6-position.
Supporting information
CCDC reference: 245283
Key indicators
- Single-crystal X-ray study
- T = 295 K
- Mean (C-C) = 0.004 Å
- R factor = 0.047
- wR factor = 0.131
- Data-to-parameter ratio = 19.3
checkCIF/PLATON results
No syntax errors found
No errors found in this datablock
Data collection: MSC/AFC-7 Diffractometer Control Software for Windows
(Molecular Structure Corporation, 1999); cell refinement: MSC/AFC-7 Diffractometer Control Software for Windows; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 1997-2001); program(s) used to solve structure: TEXSAN for Windows; program(s) used to refine structure: TEXSAN for Windows and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2001) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows and PLATON.
(1RS,2SR,6SR,8SR)-2,6-Dimethyl-8-(phenylsulfonyl)bicyclo[4.2.0]octan-1-ol
top
Crystal data top
C16H22O3S | F(000) = 632 |
Mr = 294.41 | Dx = 1.274 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71069 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 11.340 (3) Å | θ = 12.6–17.4° |
b = 18.026 (6) Å | µ = 0.22 mm−1 |
c = 7.8442 (16) Å | T = 295 K |
β = 106.788 (18)° | Prismatic, colorless |
V = 1535.1 (7) Å3 | 0.40 × 0.35 × 0.20 mm |
Z = 4 | |
Data collection top
Rigaku AFC7R diffractometer | Rint = 0.053 |
Radiation source: Rigaku rotating anode | θmax = 27.5°, θmin = 2.9° |
Graphite monochromator | h = −6→14 |
ω–2θ scans | k = −23→10 |
4336 measured reflections | l = −10→9 |
3518 independent reflections | 3 standard reflections every 150 reflections |
1904 reflections with I > 2σ(I) | intensity decay: 0.8% |
Refinement top
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)] = 0.047 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.131 | H-atom parameters constrained |
S = 1.00 | w = 1/[σ2(Fo2) + (0.0382P)2 + 0.7618P] where P = (Fo2 + 2Fc2)/3 |
3518 reflections | (Δ/σ)max = 0.001 |
182 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
Special details top
Experimental. The scan width was (1.73 + 0.30tanθ)° with an ω scan speed of 32° per minute
(up to 4 scans to achieve I/σ(I) > 10). Stationary background counts were
recorded at each end of the scan, and the scan time:background time ratio was
2:1. |
Geometry. Bond distances, angles etc. have been calculated using the rounded
fractional coordinates. All e.s.d.'s are estimated from the variances of the
(full) variance-covariance matrix. The cell e.s.d.'s are taken into account in
the estimation of distances, angles and torsion angles |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
S1 | 0.90969 (6) | 0.16012 (4) | 0.39004 (9) | 0.0456 (2) | |
O1 | 0.71411 (18) | 0.03138 (11) | 0.2793 (2) | 0.0507 (7) | |
O2 | 0.90428 (19) | 0.10497 (14) | 0.5212 (2) | 0.0692 (9) | |
O3 | 0.85807 (19) | 0.23176 (14) | 0.4021 (3) | 0.0756 (9) | |
C1 | 0.7226 (2) | 0.07423 (14) | 0.1306 (3) | 0.0341 (8) | |
C2 | 0.5979 (2) | 0.10972 (15) | 0.0463 (4) | 0.0446 (9) | |
C3 | 0.5818 (3) | 0.1358 (2) | −0.1426 (4) | 0.0658 (11) | |
C4 | 0.6154 (3) | 0.0759 (2) | −0.2569 (4) | 0.0730 (13) | |
C5 | 0.7501 (3) | 0.05653 (19) | −0.1807 (4) | 0.0574 (11) | |
C6 | 0.7821 (2) | 0.02628 (15) | 0.0098 (3) | 0.0410 (8) | |
C7 | 0.9097 (2) | 0.05481 (16) | 0.1220 (4) | 0.0457 (10) | |
C8 | 0.8440 (2) | 0.12203 (14) | 0.1755 (3) | 0.0341 (8) | |
C9 | 1.0664 (2) | 0.17158 (14) | 0.4001 (3) | 0.0373 (8) | |
C10 | 1.1041 (3) | 0.23599 (17) | 0.3343 (4) | 0.0510 (10) | |
C11 | 1.2270 (3) | 0.24290 (19) | 0.3410 (4) | 0.0596 (11) | |
C12 | 1.3087 (3) | 0.18687 (19) | 0.4123 (4) | 0.0536 (10) | |
C13 | 1.2708 (2) | 0.12324 (18) | 0.4775 (4) | 0.0507 (10) | |
C14 | 1.1482 (2) | 0.11496 (15) | 0.4713 (3) | 0.0436 (9) | |
C21 | 0.5701 (3) | 0.1701 (2) | 0.1637 (5) | 0.0705 (13) | |
C61 | 0.7603 (3) | −0.05727 (17) | 0.0121 (4) | 0.0588 (11) | |
H1 | 0.76390 | 0.05360 | 0.38670 | 0.0590* | |
H2 | 0.53820 | 0.07190 | 0.03910 | 0.0540* | |
H8 | 0.83520 | 0.16000 | 0.08870 | 0.0410* | |
H10 | 1.04700 | 0.27440 | 0.28580 | 0.0610* | |
H11 | 1.25500 | 0.28640 | 0.29630 | 0.0720* | |
H12 | 1.39280 | 0.19230 | 0.41670 | 0.0640* | |
H13 | 1.32830 | 0.08510 | 0.52640 | 0.0610* | |
H14 | 1.12070 | 0.07110 | 0.51540 | 0.0520* | |
H31 | 0.63320 | 0.17770 | −0.13950 | 0.0790* | |
H32 | 0.49820 | 0.14950 | −0.19440 | 0.0790* | |
H41 | 0.60090 | 0.09360 | −0.37520 | 0.0880* | |
H42 | 0.56660 | 0.03300 | −0.25740 | 0.0880* | |
H51 | 0.79750 | 0.10000 | −0.18050 | 0.0690* | |
H52 | 0.77070 | 0.02000 | −0.25460 | 0.0690* | |
H71 | 0.96450 | 0.06700 | 0.05470 | 0.0550* | |
H72 | 0.95050 | 0.02340 | 0.21830 | 0.0550* | |
H211 | 0.48570 | 0.18370 | 0.12070 | 0.0850* | |
H212 | 0.58720 | 0.15240 | 0.28230 | 0.0850* | |
H213 | 0.62010 | 0.21220 | 0.16140 | 0.0850* | |
H611 | 0.67540 | −0.06750 | −0.04080 | 0.0710* | |
H612 | 0.80760 | −0.08180 | −0.05310 | 0.0710* | |
H613 | 0.78440 | −0.07450 | 0.13160 | 0.0710* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
S1 | 0.0408 (3) | 0.0594 (5) | 0.0370 (3) | 0.0010 (4) | 0.0119 (3) | −0.0105 (3) |
O1 | 0.0622 (12) | 0.0466 (12) | 0.0495 (11) | −0.0070 (10) | 0.0262 (10) | 0.0115 (9) |
O2 | 0.0611 (13) | 0.111 (2) | 0.0369 (11) | −0.0165 (13) | 0.0162 (10) | 0.0112 (12) |
O3 | 0.0557 (13) | 0.0799 (17) | 0.0855 (16) | 0.0164 (12) | 0.0114 (11) | −0.0450 (14) |
C1 | 0.0346 (13) | 0.0325 (14) | 0.0388 (13) | −0.0013 (11) | 0.0165 (11) | 0.0044 (11) |
C2 | 0.0346 (13) | 0.0380 (15) | 0.0600 (17) | 0.0004 (12) | 0.0119 (12) | −0.0001 (13) |
C3 | 0.0522 (18) | 0.066 (2) | 0.064 (2) | 0.0014 (16) | −0.0074 (15) | 0.0136 (17) |
C4 | 0.075 (2) | 0.097 (3) | 0.0397 (17) | −0.017 (2) | 0.0048 (16) | 0.0026 (18) |
C5 | 0.0638 (19) | 0.070 (2) | 0.0437 (16) | −0.0172 (16) | 0.0239 (14) | −0.0114 (15) |
C6 | 0.0377 (13) | 0.0421 (16) | 0.0472 (15) | −0.0042 (12) | 0.0188 (12) | −0.0088 (12) |
C7 | 0.0345 (14) | 0.0555 (19) | 0.0512 (17) | −0.0013 (13) | 0.0191 (12) | −0.0111 (14) |
C8 | 0.0332 (12) | 0.0376 (15) | 0.0327 (12) | −0.0024 (11) | 0.0114 (10) | −0.0004 (11) |
C9 | 0.0383 (13) | 0.0404 (15) | 0.0298 (12) | −0.0016 (12) | 0.0046 (10) | −0.0039 (11) |
C10 | 0.0552 (17) | 0.0458 (18) | 0.0460 (16) | 0.0023 (14) | 0.0051 (13) | 0.0086 (14) |
C11 | 0.0599 (19) | 0.061 (2) | 0.0573 (19) | −0.0135 (16) | 0.0159 (16) | 0.0137 (16) |
C12 | 0.0416 (15) | 0.067 (2) | 0.0520 (17) | −0.0093 (15) | 0.0131 (13) | −0.0077 (15) |
C13 | 0.0412 (15) | 0.0508 (19) | 0.0540 (17) | 0.0027 (14) | 0.0040 (13) | −0.0076 (14) |
C14 | 0.0443 (15) | 0.0398 (16) | 0.0420 (15) | −0.0035 (12) | 0.0049 (12) | 0.0016 (12) |
C21 | 0.0501 (18) | 0.068 (2) | 0.092 (3) | 0.0195 (17) | 0.0185 (17) | −0.0139 (19) |
C61 | 0.0559 (18) | 0.0437 (19) | 0.081 (2) | −0.0034 (14) | 0.0264 (16) | −0.0144 (16) |
Geometric parameters (Å, º) top
S1—O2 | 1.445 (2) | C13—C14 | 1.385 (3) |
S1—O3 | 1.432 (3) | C2—H2 | 0.9509 |
S1—C8 | 1.770 (2) | C3—H31 | 0.9501 |
S1—C9 | 1.768 (3) | C3—H32 | 0.9499 |
O1—C1 | 1.425 (3) | C4—H41 | 0.9496 |
O1—H1 | 0.9561 | C4—H42 | 0.9503 |
C1—C2 | 1.519 (4) | C5—H51 | 0.9500 |
C1—C6 | 1.571 (3) | C5—H52 | 0.9500 |
C1—C8 | 1.575 (3) | C7—H71 | 0.9501 |
C2—C21 | 1.517 (5) | C7—H72 | 0.9505 |
C2—C3 | 1.514 (4) | C8—H8 | 0.9501 |
C3—C4 | 1.521 (5) | C10—H10 | 0.9493 |
C4—C5 | 1.512 (5) | C11—H11 | 0.9502 |
C5—C6 | 1.533 (4) | C12—H12 | 0.9494 |
C6—C7 | 1.548 (4) | C13—H13 | 0.9489 |
C6—C61 | 1.527 (4) | C14—H14 | 0.9510 |
C7—C8 | 1.543 (4) | C21—H211 | 0.9505 |
C9—C14 | 1.384 (4) | C21—H212 | 0.9490 |
C9—C10 | 1.387 (4) | C21—H213 | 0.9506 |
C10—C11 | 1.385 (5) | C61—H611 | 0.9499 |
C11—C12 | 1.375 (5) | C61—H612 | 0.9504 |
C12—C13 | 1.374 (5) | C61—H613 | 0.9497 |
| | | |
S1···H1 | 2.5290 | H8···H31 | 2.4869 |
O1···O2 | 2.765 (3) | H8···H51 | 2.3000 |
O1···C13i | 3.354 (4) | H8···O3vii | 2.4972 |
O1···C14i | 3.385 (3) | H10···O3 | 2.6725 |
O2···O1 | 2.765 (3) | H11···C13vii | 3.0328 |
O2···C5ii | 3.413 (4) | H11···C14vii | 3.0568 |
O1···H613 | 2.4807 | H13···O1i | 2.7178 |
O1···H13i | 2.7178 | H14···O2 | 2.5421 |
O1···H14i | 2.7879 | H14···O1i | 2.7879 |
O1···H72 | 2.8595 | H31···C8 | 3.0684 |
O1···H212 | 2.6173 | H31···H8 | 2.4869 |
O2···H1 | 1.8800 | H31···H51 | 2.4254 |
O2···H14 | 2.5421 | H31···H213 | 2.4865 |
O3···H10 | 2.6725 | H31···H213vii | 2.5032 |
O3···H213 | 2.8334 | H32···H211 | 2.5907 |
O3···H8iii | 2.4972 | H42···C61 | 3.0429 |
C5···O2iv | 3.413 (4) | H42···H2 | 2.5372 |
C7···C14 | 3.423 (4) | H42···H611 | 2.5456 |
C13···O1i | 3.354 (4) | H51···C8 | 2.7172 |
C14···O1i | 3.385 (3) | H51···H8 | 2.3000 |
C14···C7 | 3.423 (4) | H51···H31 | 2.4254 |
C3···H8 | 2.9543 | H51···H71 | 2.3078 |
C4···H611 | 3.0581 | H52···H612 | 2.3788 |
C5···H8 | 2.7745 | H52···C13v | 3.0774 |
C7···H1 | 3.0047 | H71···H51 | 2.3078 |
C8···H213 | 2.9897 | H72···O1 | 2.8595 |
C8···H51 | 2.7172 | H72···C14 | 3.0197 |
C8···H31 | 3.0684 | H72···H613 | 2.5268 |
C13···H52v | 3.0774 | H211···H32 | 2.5907 |
C13···H11iii | 3.0328 | H212···O1 | 2.6173 |
C14···H72 | 3.0197 | H213···O3 | 2.8334 |
C14···H613i | 3.0730 | H213···C8 | 2.9897 |
C14···H11iii | 3.0568 | H213···H31 | 2.4865 |
C61···H42 | 3.0429 | H213···H31iii | 2.5032 |
H1···S1 | 2.5290 | H611···C4 | 3.0581 |
H1···O2 | 1.8800 | H611···H42 | 2.5456 |
H1···C7 | 3.0047 | H611···H2vi | 2.4274 |
H2···H42 | 2.5372 | H612···H52 | 2.3788 |
H2···H611vi | 2.4274 | H613···O1 | 2.4807 |
H8···C3 | 2.9543 | H613···H72 | 2.5268 |
H8···C5 | 2.7745 | H613···C14i | 3.0730 |
| | | |
O2—S1—O3 | 118.11 (14) | C4—C3—H32 | 108.75 |
O2—S1—C8 | 108.50 (12) | H31—C3—H32 | 109.47 |
O2—S1—C9 | 107.31 (12) | C3—C4—H41 | 109.60 |
O3—S1—C8 | 110.16 (13) | C3—C4—H42 | 109.60 |
O3—S1—C9 | 108.45 (13) | C5—C4—H41 | 109.51 |
C8—S1—C9 | 103.25 (11) | C5—C4—H42 | 109.54 |
C1—O1—H1 | 109.38 | H41—C4—H42 | 109.46 |
O1—C1—C6 | 109.7 (2) | C4—C5—H51 | 108.47 |
O1—C1—C8 | 112.01 (18) | C4—C5—H52 | 108.50 |
C2—C1—C6 | 118.5 (2) | C6—C5—H51 | 108.50 |
C2—C1—C8 | 120.7 (2) | C6—C5—H52 | 108.52 |
C6—C1—C8 | 86.33 (17) | H51—C5—H52 | 109.51 |
O1—C1—C2 | 108.1 (2) | C6—C7—H71 | 114.51 |
C1—C2—C3 | 113.0 (2) | C6—C7—H72 | 114.48 |
C1—C2—C21 | 111.6 (2) | C8—C7—H71 | 114.47 |
C3—C2—C21 | 112.6 (3) | C8—C7—H72 | 114.47 |
C2—C3—C4 | 112.1 (3) | H71—C7—H72 | 109.45 |
C3—C4—C5 | 109.1 (3) | S1—C8—H8 | 109.27 |
C4—C5—C6 | 113.3 (3) | C1—C8—H8 | 109.25 |
C1—C6—C7 | 88.17 (18) | C7—C8—H8 | 109.26 |
C1—C6—C61 | 115.9 (2) | C9—C10—H10 | 120.78 |
C1—C6—C5 | 111.7 (2) | C11—C10—H10 | 120.80 |
C5—C6—C61 | 111.6 (2) | C10—C11—H11 | 120.00 |
C7—C6—C61 | 116.7 (2) | C12—C11—H11 | 119.89 |
C5—C6—C7 | 110.8 (2) | C11—C12—H12 | 119.38 |
C6—C7—C8 | 88.28 (18) | C13—C12—H12 | 119.43 |
S1—C8—C1 | 121.69 (16) | C12—C13—H13 | 120.19 |
C1—C8—C7 | 88.23 (18) | C14—C13—H13 | 120.11 |
S1—C8—C7 | 117.36 (18) | C9—C14—H14 | 120.53 |
S1—C9—C10 | 119.7 (2) | C13—C14—H14 | 120.54 |
C10—C9—C14 | 121.7 (2) | C2—C21—H211 | 109.53 |
S1—C9—C14 | 118.67 (19) | C2—C21—H212 | 109.54 |
C9—C10—C11 | 118.4 (3) | C2—C21—H213 | 109.37 |
C10—C11—C12 | 120.1 (3) | H211—C21—H212 | 109.53 |
C11—C12—C13 | 121.2 (3) | H211—C21—H213 | 109.41 |
C12—C13—C14 | 119.7 (3) | H212—C21—H213 | 109.44 |
C9—C14—C13 | 118.9 (2) | C6—C61—H611 | 109.47 |
C1—C2—H2 | 106.34 | C6—C61—H612 | 109.51 |
C3—C2—H2 | 106.37 | C6—C61—H613 | 109.44 |
C21—C2—H2 | 106.34 | H611—C61—H612 | 109.45 |
C2—C3—H31 | 108.79 | H611—C61—H613 | 109.52 |
C2—C3—H32 | 108.82 | H612—C61—H613 | 109.44 |
C4—C3—H31 | 108.86 | | |
| | | |
O2—S1—C8—C1 | 42.2 (2) | C8—C1—C6—C5 | −89.5 (2) |
O2—S1—C8—C7 | −64.0 (2) | C8—C1—C6—C7 | 22.17 (18) |
O3—S1—C8—C1 | −88.5 (2) | C8—C1—C6—C61 | 141.1 (2) |
O3—S1—C8—C7 | 165.31 (19) | O1—C1—C8—S1 | −33.8 (3) |
C9—S1—C8—C1 | 155.83 (19) | C2—C1—C6—C7 | 145.4 (2) |
C9—S1—C8—C7 | 49.7 (2) | C2—C1—C6—C61 | −95.7 (3) |
O2—S1—C9—C10 | −159.0 (2) | C1—C2—C3—C4 | 49.8 (3) |
O2—S1—C9—C14 | 22.1 (2) | C21—C2—C3—C4 | 177.5 (3) |
O3—S1—C9—C10 | −30.4 (2) | C2—C3—C4—C5 | −62.5 (4) |
O3—S1—C9—C14 | 150.7 (2) | C3—C4—C5—C6 | 60.9 (4) |
C8—S1—C9—C10 | 86.5 (2) | C4—C5—C6—C1 | −45.7 (3) |
C8—S1—C9—C14 | −92.5 (2) | C4—C5—C6—C61 | 85.8 (3) |
C6—C1—C2—C3 | −36.0 (3) | C4—C5—C6—C7 | −142.3 (3) |
O1—C1—C2—C21 | 70.3 (3) | C1—C6—C7—C8 | −22.62 (18) |
O1—C1—C6—C61 | 29.0 (3) | C61—C6—C7—C8 | −140.8 (2) |
C2—C1—C6—C5 | 33.6 (3) | C5—C6—C7—C8 | 90.0 (2) |
C6—C1—C2—C21 | −164.1 (2) | C6—C7—C8—S1 | 147.71 (18) |
C8—C1—C2—C3 | 67.7 (3) | C6—C7—C8—C1 | 22.56 (18) |
C8—C1—C2—C21 | −60.4 (3) | S1—C9—C10—C11 | −178.9 (2) |
O1—C1—C6—C5 | 158.4 (2) | C10—C9—C14—C13 | 0.3 (4) |
O1—C1—C6—C7 | −89.9 (2) | C14—C9—C10—C11 | 0.0 (4) |
O1—C1—C2—C3 | −161.6 (2) | S1—C9—C14—C13 | 179.2 (2) |
O1—C1—C8—C7 | 87.6 (2) | C9—C10—C11—C12 | −0.3 (4) |
C2—C1—C8—S1 | 95.1 (3) | C10—C11—C12—C13 | 0.2 (5) |
C2—C1—C8—C7 | −143.4 (2) | C11—C12—C13—C14 | 0.2 (5) |
C6—C1—C8—S1 | −143.66 (19) | C12—C13—C14—C9 | −0.4 (4) |
C6—C1—C8—C7 | −22.25 (18) | | |
Symmetry codes: (i) −x+2, −y, −z+1; (ii) x, y, z+1; (iii) x, −y+1/2, z+1/2; (iv) x, y, z−1; (v) −x+2, −y, −z; (vi) −x+1, −y, −z; (vii) x, −y+1/2, z−1/2. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1—H1···O2 | 0.9600 | 1.8800 | 2.765 (3) | 153.00 |
C8—H8···O3vii | 0.9500 | 2.5000 | 3.431 (4) | 167.00 |
C14—H14···O2 | 0.9500 | 2.5400 | 2.909 (3) | 103.00 |
Symmetry code: (vii) x, −y+1/2, z−1/2. |