Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802002878/tk6056sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536802002878/tk6056Isup2.hkl |
CCDC reference: 182628
Compounds (I) and (II) were prepared by the reaction of acetophenone (0.50 g, 0.49 ml, 4.20 mmol) in THF (5 ml) with lithium diisopropylamide (1.7 M, 4.60 mmol, 2.70 ml) in THF (30 ml) at 195 K under nitrogen over 10 min. Rapid addition of phenyl vinyl sulfoxide (0.63 g, 0.56 ml, 4.20 mmol) at 243 K with a 5 min reaction time and workup as described elsewhere (Loughlin et al., 2002) was followed by purification by silica column chromatography (diethyl ether). Fraction 1 (299 mg) contained a 72:28 mixture of unreacted phenylvinyl sulfoxide and (I). Fraction 2 contained (II) (46 mg), m.p. 349–350 K. Suspension of fraction one in ether, filtration and recrystallization (ether) gave (I) as a white solid (m.p. 397–399 K). Crystals of (I) were isolated as colorless plates by slow evaporation of a solution of the pure compound in ether.
H atoms were located at calculated positions with C—H set to 0.95 Å. Hydroxyl H atoms on O1 and O3 were located from difference synthesis and O—H was set to 0.95 Å. All H atoms were constrained in the refinement. Due to a large fraction of weak data at higher angles, the 2θ maximum was limited to 50°.
Data collection: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999); cell refinement: MSC/AFC7 Diffractometer Control Software; data reduction: TEXSAN for Windows (Molecular Structure Corporation, 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, 1980-2001) and ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: TEXSAN for Windows and PLATON (Spek, 2001).
C16H16O2S | F(000) = 1152 |
Mr = 272.36 | Dx = 1.285 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.7107 Å |
Hall symbol: -P 2ybc | Cell parameters from 25 reflections |
a = 10.439 (2) Å | θ = 12.5–16.1° |
b = 17.361 (3) Å | µ = 0.23 mm−1 |
c = 15.555 (2) Å | T = 295 K |
β = 92.74 (1)° | Plate, colorless |
V = 2815.8 (7) Å3 | 0.50 × 0.20 × 0.20 mm |
Z = 8 |
Rigaku AFC-7R diffractometer | Rint = 0.044 |
Radiation source: Rigaku rotating anode | θmax = 25.0°, θmin = 2.6° |
Graphite monochromator | h = −12→7 |
ω–2θ scans | k = −20→0 |
6253 measured reflections | l = −18→18 |
4965 independent reflections | 3 standard reflections every 150 reflections |
2695 reflections with I > 2σ(I) | intensity decay: 1.7% |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.047 | H-atom parameters not refined |
wR(F2) = 0.138 | w = 1/[σ2(Fo2) + (0.0509P)2 + 0.6926P] where P = (Fo2 + 2Fc2)/3 |
S = 1.00 | (Δ/σ)max = 0.001 |
4965 reflections | Δρmax = 0.32 e Å−3 |
344 parameters | Δρmin = −0.28 e Å−3 |
0 restraints | Extinction correction: SHELXL97, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0017 (4) |
C16H16O2S | V = 2815.8 (7) Å3 |
Mr = 272.36 | Z = 8 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.439 (2) Å | µ = 0.23 mm−1 |
b = 17.361 (3) Å | T = 295 K |
c = 15.555 (2) Å | 0.50 × 0.20 × 0.20 mm |
β = 92.74 (1)° |
Rigaku AFC-7R diffractometer | Rint = 0.044 |
6253 measured reflections | 3 standard reflections every 150 reflections |
4965 independent reflections | intensity decay: 1.7% |
2695 reflections with I > 2σ(I) |
R[F2 > 2σ(F2)] = 0.047 | 0 restraints |
wR(F2) = 0.138 | H-atom parameters not refined |
S = 1.00 | Δρmax = 0.32 e Å−3 |
4965 reflections | Δρmin = −0.28 e Å−3 |
344 parameters |
Experimental. (1RSc,2RSc,RSs-1-phenyl-2-phenylsulfinylcyclobutan-1-ol (I) (Found: C 70.63, H 5.96, S 11.63%. C16H16O2S requires C 70.56, H 5.92, S 11.77%); υmax (KBr)/cm-1 3424 (m), 1026 (m); δH (400 MHz, CDCl3) 1.91–2.00 (1H, m, H3), 2.42–2.65 (3H, m, H3, 2 x H4), 3.67–3.74 (1H, m, H2), 4.70 (brs, Wh/2 = 15 Hz), 7.18–7.23 (1H, m, p-C6H5), 7.25–7.30(2H, m, m-C6H5), 7.36–7.40 (2H, m, o-C6H5), 7.42–7.47(3H, m, m-,p-C6H5S(O)), 7.61–7.67 (2H, m, o-C6H5S(O)); δC (100 MHz) 17.0 (C3), 34.3 (C4), 66.3 (C2), 80.8 (C1), 124.8 ((o-C6H5S(O)), 125.2 (o-C6H5), 127.5 (p-C6H5), 128.4 (m-C6H5), 129.1 (m-C6H5S(O)), 131.1 (p-C6H5S(O)), 141.6 (i-C6H5), 144.5 (i-C6H5S(O)); (ESMS +ve) 295 (MNa+). 4-phenylsulfinyl-1-phenylbutan-1-one (II) (Found: C 70.44, H 5.94, S 11.56%. C16H16O2S requires C 70.56, H 5.92, S 11.77%). υmax (KBr)/cm-1 1684 (s), 1040 (m); δH (400 MHz, CDCl3) 2.02–2.27 (2H, m, 2 x H3), 2.81–2.99 (2H, m, 2 x H4), 3.13 (ddd, J2,3 2.5, J2,3 7.0, J2,2 9.0 Hz, 2 x H2), 7.39–7.56,(6H, m, m-, p-C6H5, m- p-C6H5S(O)), 7.58–7.63(2H, m, o-C6H5S(O)), 7.86–7.93 (2H, m, o-C6H5); δC (100 MHz) 17.0 (C3), 36.8 (C2), 56.2 (C4), 124.0 ((o-C6H5S(O)), 127.9 (o-C6H5), 128.6 (m-C6H5), 129.2 (m-C6H5S(O)), 131.0 (p-C6H5S(O)), 133.3 (p-C6H5), 136.5 (i-C6H5), 143.6 (i-C6H5S(O)), 198.6 (C1); (ESMS +ve) 295 (MNa+). The scan width was (1.63 + 0.30tanθ)° with an ω scan speed of 16° per minute (up to 5 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 on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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 | ||
S1A | 0.79928 (8) | 0.69293 (5) | 0.35768 (5) | 0.0451 (3) | |
O1A | 0.9664 (2) | 0.60198 (13) | 0.24917 (13) | 0.0487 (8) | |
O2A | 0.6831 (2) | 0.64990 (14) | 0.38683 (15) | 0.0569 (9) | |
C1A | 0.9925 (3) | 0.57687 (19) | 0.33574 (19) | 0.0417 (11) | |
C2A | 0.9366 (3) | 0.63804 (19) | 0.39665 (19) | 0.0411 (10) | |
C3A | 1.0672 (3) | 0.6787 (2) | 0.3998 (2) | 0.0568 (12) | |
C4A | 1.1268 (3) | 0.6032 (2) | 0.3701 (2) | 0.0526 (11) | |
C5A | 0.9555 (3) | 0.49321 (19) | 0.34484 (19) | 0.0437 (11) | |
C6A | 1.0421 (4) | 0.4366 (2) | 0.3237 (2) | 0.0593 (16) | |
C7A | 1.0092 (5) | 0.3594 (2) | 0.3282 (3) | 0.0734 (19) | |
C8A | 0.8898 (6) | 0.3386 (2) | 0.3537 (3) | 0.0792 (18) | |
C9A | 0.8027 (5) | 0.3943 (3) | 0.3737 (3) | 0.0787 (17) | |
C10A | 0.8361 (4) | 0.4720 (2) | 0.3692 (2) | 0.0596 (14) | |
C11A | 0.8245 (3) | 0.77323 (19) | 0.4281 (2) | 0.0434 (11) | |
C12A | 0.8322 (4) | 0.7639 (2) | 0.5167 (2) | 0.0527 (12) | |
C13A | 0.8547 (4) | 0.8265 (2) | 0.5694 (2) | 0.0599 (16) | |
C14A | 0.8696 (4) | 0.8985 (2) | 0.5330 (3) | 0.0604 (16) | |
C15A | 0.8604 (4) | 0.9085 (2) | 0.4461 (3) | 0.0651 (16) | |
C16A | 0.8379 (4) | 0.8452 (2) | 0.3924 (2) | 0.0567 (12) | |
S1B | 0.70971 (9) | 0.36215 (5) | 0.86351 (5) | 0.0491 (3) | |
O1B | 0.5183 (2) | 0.37630 (13) | 0.72455 (15) | 0.0546 (9) | |
O2B | 0.8268 (2) | 0.41112 (16) | 0.85136 (16) | 0.0671 (10) | |
C1B | 0.5077 (3) | 0.44483 (18) | 0.7724 (2) | 0.0405 (11) | |
C2B | 0.5784 (3) | 0.42940 (18) | 0.8622 (2) | 0.0413 (11) | |
C3B | 0.4495 (3) | 0.4050 (2) | 0.8969 (2) | 0.0604 (14) | |
C4B | 0.3823 (3) | 0.4473 (2) | 0.8204 (2) | 0.0514 (11) | |
C5B | 0.5436 (3) | 0.5155 (2) | 0.7219 (2) | 0.0485 (11) | |
C6B | 0.5686 (4) | 0.5107 (3) | 0.6356 (3) | 0.0710 (17) | |
C7B | 0.5966 (5) | 0.5763 (4) | 0.5891 (4) | 0.103 (3) | |
C8B | 0.5992 (5) | 0.6469 (4) | 0.6291 (6) | 0.117 (3) | |
C9B | 0.5757 (5) | 0.6532 (3) | 0.7147 (5) | 0.098 (2) | |
C10B | 0.5478 (4) | 0.5875 (2) | 0.7614 (3) | 0.0668 (17) | |
C11B | 0.7091 (3) | 0.33940 (18) | 0.9753 (2) | 0.0434 (11) | |
C12B | 0.7807 (3) | 0.38115 (19) | 1.0354 (2) | 0.0494 (12) | |
C13B | 0.7755 (4) | 0.3624 (3) | 1.1214 (2) | 0.0675 (16) | |
C14B | 0.6995 (5) | 0.3039 (3) | 1.1470 (3) | 0.0829 (19) | |
C15B | 0.6289 (4) | 0.2614 (3) | 1.0878 (4) | 0.0865 (19) | |
C16B | 0.6344 (4) | 0.2780 (2) | 1.0010 (3) | 0.0669 (14) | |
H1A | 1.03920 | 0.59270 | 0.21630 | 0.0650* | |
H2A | 0.92110 | 0.61580 | 0.45090 | 0.0490* | |
H6A | 1.12470 | 0.45080 | 0.30610 | 0.0710* | |
H7A | 1.06910 | 0.32100 | 0.31360 | 0.0880* | |
H8A | 0.86750 | 0.28570 | 0.35750 | 0.0950* | |
H9A | 0.71980 | 0.38000 | 0.39060 | 0.0940* | |
H10A | 0.77560 | 0.51040 | 0.38320 | 0.0710* | |
H12A | 0.82200 | 0.71420 | 0.54100 | 0.0630* | |
H13A | 0.86000 | 0.82040 | 0.63020 | 0.0720* | |
H14A | 0.88660 | 0.94160 | 0.56930 | 0.0720* | |
H15A | 0.86920 | 0.95850 | 0.42230 | 0.0780* | |
H16A | 0.83200 | 0.85170 | 0.33170 | 0.0680* | |
H31A | 1.07310 | 0.72020 | 0.36040 | 0.0680* | |
H32A | 1.09650 | 0.69520 | 0.45560 | 0.0680* | |
H41A | 1.18740 | 0.60930 | 0.32690 | 0.0630* | |
H42A | 1.16300 | 0.57240 | 0.41540 | 0.0630* | |
H1B | 0.44300 | 0.37030 | 0.68720 | 0.0700* | |
H2B | 0.60580 | 0.47670 | 0.88780 | 0.0500* | |
H6B | 0.56660 | 0.46200 | 0.60780 | 0.0850* | |
H7B | 0.61400 | 0.57240 | 0.52990 | 0.1240* | |
H8B | 0.61750 | 0.69180 | 0.59700 | 0.1400* | |
H9B | 0.57830 | 0.70220 | 0.74200 | 0.1180* | |
H10B | 0.53160 | 0.59170 | 0.82080 | 0.0800* | |
H12B | 0.83320 | 0.42240 | 1.01790 | 0.0590* | |
H13B | 0.82550 | 0.39070 | 1.16320 | 0.0810* | |
H14B | 0.69540 | 0.29240 | 1.20650 | 0.1000* | |
H15B | 0.57620 | 0.22050 | 1.10620 | 0.1040* | |
H16B | 0.58760 | 0.24780 | 0.95940 | 0.0800* | |
H31B | 0.43550 | 0.35100 | 0.89740 | 0.0720* | |
H32B | 0.43260 | 0.42590 | 0.95160 | 0.0720* | |
H41B | 0.31360 | 0.41920 | 0.79300 | 0.0620* | |
H42B | 0.35400 | 0.49780 | 0.83340 | 0.0620* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1A | 0.0455 (5) | 0.0509 (5) | 0.0382 (4) | 0.0043 (4) | −0.0052 (4) | −0.0046 (4) |
O1A | 0.0484 (14) | 0.0635 (16) | 0.0347 (12) | 0.0043 (12) | 0.0058 (10) | 0.0055 (10) |
O2A | 0.0386 (13) | 0.0660 (17) | 0.0655 (16) | −0.0046 (12) | −0.0025 (11) | −0.0129 (13) |
C1A | 0.0385 (18) | 0.052 (2) | 0.0342 (17) | 0.0008 (16) | −0.0016 (14) | 0.0013 (15) |
C2A | 0.0422 (18) | 0.0464 (19) | 0.0343 (16) | 0.0010 (16) | −0.0011 (14) | 0.0013 (15) |
C3A | 0.039 (2) | 0.062 (2) | 0.069 (2) | −0.0055 (19) | −0.0024 (17) | −0.008 (2) |
C4A | 0.0345 (18) | 0.066 (2) | 0.057 (2) | −0.0017 (18) | 0.0002 (16) | −0.0033 (19) |
C5A | 0.051 (2) | 0.046 (2) | 0.0337 (18) | 0.0004 (17) | −0.0029 (15) | 0.0004 (15) |
C6A | 0.065 (3) | 0.056 (3) | 0.057 (2) | 0.008 (2) | 0.0024 (19) | 0.0005 (19) |
C7A | 0.100 (4) | 0.053 (3) | 0.066 (3) | 0.012 (3) | −0.007 (2) | 0.002 (2) |
C8A | 0.117 (4) | 0.045 (2) | 0.074 (3) | −0.013 (3) | −0.012 (3) | 0.009 (2) |
C9A | 0.081 (3) | 0.065 (3) | 0.090 (3) | −0.020 (3) | 0.003 (3) | 0.014 (2) |
C10A | 0.061 (3) | 0.056 (2) | 0.062 (2) | −0.007 (2) | 0.004 (2) | 0.0079 (19) |
C11A | 0.0402 (19) | 0.043 (2) | 0.047 (2) | 0.0012 (15) | 0.0009 (15) | −0.0056 (16) |
C12A | 0.065 (2) | 0.048 (2) | 0.045 (2) | −0.0031 (19) | 0.0025 (17) | −0.0042 (17) |
C13A | 0.068 (3) | 0.059 (3) | 0.052 (2) | 0.007 (2) | −0.0032 (19) | −0.0091 (19) |
C14A | 0.048 (2) | 0.056 (3) | 0.076 (3) | 0.0064 (19) | −0.008 (2) | −0.020 (2) |
C15A | 0.067 (3) | 0.044 (2) | 0.084 (3) | 0.008 (2) | 0.002 (2) | 0.001 (2) |
C16A | 0.064 (2) | 0.052 (2) | 0.054 (2) | 0.0082 (19) | 0.0012 (18) | 0.0039 (18) |
S1B | 0.0480 (5) | 0.0545 (6) | 0.0446 (5) | 0.0140 (5) | 0.0009 (4) | −0.0029 (4) |
O1B | 0.0519 (15) | 0.0525 (15) | 0.0580 (15) | 0.0117 (12) | −0.0134 (12) | −0.0182 (12) |
O2B | 0.0401 (15) | 0.099 (2) | 0.0634 (17) | 0.0040 (14) | 0.0145 (12) | 0.0179 (15) |
C1B | 0.0351 (18) | 0.044 (2) | 0.0423 (18) | 0.0058 (15) | −0.0005 (15) | −0.0068 (15) |
C2B | 0.0380 (18) | 0.0392 (19) | 0.0470 (19) | 0.0048 (16) | 0.0061 (15) | −0.0001 (15) |
C3B | 0.047 (2) | 0.077 (3) | 0.058 (2) | 0.010 (2) | 0.0116 (18) | 0.013 (2) |
C4B | 0.0373 (19) | 0.053 (2) | 0.064 (2) | 0.0012 (17) | 0.0041 (17) | −0.0011 (18) |
C5B | 0.0341 (19) | 0.057 (2) | 0.054 (2) | 0.0048 (17) | −0.0029 (16) | 0.0109 (19) |
C6B | 0.058 (3) | 0.096 (3) | 0.059 (3) | 0.014 (2) | 0.004 (2) | 0.019 (2) |
C7B | 0.069 (3) | 0.151 (6) | 0.092 (4) | 0.024 (4) | 0.020 (3) | 0.066 (4) |
C8B | 0.049 (3) | 0.126 (5) | 0.175 (7) | 0.011 (3) | 0.010 (4) | 0.095 (5) |
C9B | 0.061 (3) | 0.057 (3) | 0.175 (6) | −0.004 (2) | −0.013 (4) | 0.031 (4) |
C10B | 0.060 (3) | 0.055 (3) | 0.085 (3) | 0.000 (2) | −0.002 (2) | 0.011 (2) |
C11B | 0.0410 (19) | 0.041 (2) | 0.048 (2) | 0.0094 (16) | 0.0013 (15) | 0.0056 (16) |
C12B | 0.052 (2) | 0.043 (2) | 0.053 (2) | 0.0064 (17) | −0.0003 (17) | 0.0053 (17) |
C13B | 0.083 (3) | 0.067 (3) | 0.052 (2) | 0.033 (2) | −0.002 (2) | 0.000 (2) |
C14B | 0.082 (3) | 0.103 (4) | 0.066 (3) | 0.040 (3) | 0.027 (3) | 0.034 (3) |
C15B | 0.065 (3) | 0.081 (3) | 0.115 (4) | 0.004 (3) | 0.020 (3) | 0.056 (3) |
C16B | 0.054 (2) | 0.056 (2) | 0.090 (3) | −0.006 (2) | −0.005 (2) | 0.019 (2) |
S1A—O2A | 1.512 (2) | C12A—H12A | 0.9500 |
S1A—C2A | 1.802 (3) | C13A—H13A | 0.9506 |
S1A—C11A | 1.785 (3) | C14A—H14A | 0.9490 |
S1B—O2B | 1.508 (3) | C15A—H15A | 0.9499 |
S1B—C2B | 1.800 (3) | C16A—H16A | 0.9500 |
S1B—C11B | 1.783 (3) | C1B—C2B | 1.571 (4) |
O1A—C1A | 1.429 (4) | C1B—C4B | 1.538 (4) |
O1A—H1A | 0.9498 | C1B—C5B | 1.514 (5) |
O1B—C1B | 1.411 (4) | C2B—C3B | 1.533 (4) |
O1B—H1B | 0.9605 | C3B—C4B | 1.539 (5) |
C1A—C2A | 1.555 (4) | C5B—C6B | 1.382 (6) |
C1A—C4A | 1.545 (4) | C5B—C10B | 1.393 (5) |
C1A—C5A | 1.511 (5) | C6B—C7B | 1.388 (8) |
C2A—C3A | 1.534 (5) | C7B—C8B | 1.374 (10) |
C3A—C4A | 1.532 (5) | C8B—C9B | 1.370 (12) |
C5A—C6A | 1.386 (5) | C9B—C10B | 1.391 (7) |
C5A—C10A | 1.370 (5) | C11B—C16B | 1.391 (5) |
C6A—C7A | 1.386 (5) | C11B—C12B | 1.375 (4) |
C7A—C8A | 1.374 (8) | C12B—C13B | 1.380 (5) |
C8A—C9A | 1.373 (7) | C13B—C14B | 1.360 (7) |
C9A—C10A | 1.396 (6) | C14B—C15B | 1.368 (7) |
C11A—C12A | 1.386 (4) | C15B—C16B | 1.384 (8) |
C11A—C16A | 1.377 (5) | C2B—H2B | 0.9507 |
C12A—C13A | 1.375 (5) | C3B—H31B | 0.9489 |
C13A—C14A | 1.384 (5) | C3B—H32B | 0.9493 |
C14A—C15A | 1.362 (7) | C4B—H41B | 0.9512 |
C15A—C16A | 1.393 (5) | C4B—H42B | 0.9500 |
C2A—H2A | 0.9489 | C6B—H6B | 0.9494 |
C3A—H32A | 0.9506 | C7B—H7B | 0.9495 |
C3A—H31A | 0.9498 | C8B—H8B | 0.9500 |
C4A—H42A | 0.9486 | C9B—H9B | 0.9506 |
C4A—H41A | 0.9506 | C10B—H10B | 0.9500 |
C6A—H6A | 0.9496 | C12B—H12B | 0.9495 |
C7A—H7A | 0.9490 | C13B—H13B | 0.9509 |
C8A—H8A | 0.9500 | C14B—H14B | 0.9498 |
C9A—H9A | 0.9494 | C15B—H15B | 0.9507 |
C10A—H10A | 0.9507 | C16B—H16B | 0.9498 |
S1A···O1A | 2.944 (2) | H1A···O2Biii | 1.7915 |
S1B···O1B | 2.883 (2) | H1B···H6B | 2.4243 |
S1A···H1Bi | 2.8143 | H1B···H41B | 2.3380 |
S1B···H8Aii | 3.0537 | H1B···S1Ai | 2.8143 |
S1B···H1Aiii | 3.0557 | H1B···O2Ai | 1.7427 |
O1A···S1A | 2.944 (2) | H1B···H15Bv | 2.4846 |
O1A···C13Aiv | 3.226 (4) | H1B···C6B | 2.8992 |
O1A···O2Biii | 2.735 (3) | H2A···C12A | 2.9344 |
O1B···S1B | 2.883 (2) | H2A···C10A | 2.9201 |
O1B···O2Ai | 2.698 (3) | H2A···H10A | 2.5713 |
O2A···O1Bi | 2.698 (3) | H2A···H12A | 2.4681 |
O2B···O1Aiii | 2.735 (3) | H2B···C10B | 2.7962 |
O1A···H13Aiv | 2.5055 | H2B···H10B | 2.3654 |
O1A···H31A | 2.8744 | H6A···C4A | 2.8266 |
O1B···H15Bv | 2.5855 | H6B···H1B | 2.4243 |
O1B···H31B | 2.8968 | H6B···O1B | 2.4194 |
O1B···H6B | 2.4194 | H7A···H16Axii | 2.5848 |
O2A···H7B | 2.7270 | H7A···H12Aiii | 2.5564 |
O2A···H10A | 2.6089 | H7B···O2A | 2.7270 |
O2A···H1Bi | 1.7427 | H8A···S1Bv | 3.0537 |
O2B···H1Aiii | 1.7915 | H8B···H16Bx | 2.4737 |
O2B···H41Aiii | 2.7923 | H8B···C12A | 2.9014 |
O2B···H15Avi | 2.5476 | H8B···H12A | 2.3759 |
O2B···H12B | 2.5956 | H10A···O2A | 2.6089 |
C3A···C15Bvii | 3.479 (5) | H10A···C2A | 2.7830 |
C3A···C14Bvii | 3.370 (6) | H10A···H2A | 2.5713 |
C3A···C12A | 3.455 (5) | H10B···C14Bix | 3.0776 |
C3B···C13Aviii | 3.518 (5) | H10B···C4B | 2.9518 |
C3B···C14Aviii | 3.556 (5) | H10B···H2B | 2.3654 |
C3B···C16B | 3.303 (5) | H10B···C2B | 2.9262 |
C7A···C12Aiii | 3.572 (6) | H10B···H42B | 2.4835 |
C10B···C14Bix | 3.550 (7) | H12A···C8B | 2.9929 |
C12A···C7Aiii | 3.572 (6) | H12A···H2A | 2.4681 |
C12A···C3A | 3.455 (5) | H12A···C2A | 2.9117 |
C13A···C3Bx | 3.518 (5) | H12A···H8B | 2.3759 |
C13A···O1Avi | 3.226 (4) | H12A···C7Aiii | 2.9214 |
C14A···C3Bx | 3.556 (5) | H12A···H7Aiii | 2.5564 |
C14B···C10Bix | 3.550 (7) | H12B···O2B | 2.5956 |
C14B···C3Axi | 3.370 (6) | H12B···H14Avi | 2.5460 |
C15B···C3Axi | 3.479 (5) | H12B···H15Avi | 2.5848 |
C16B···C3B | 3.303 (5) | H13A···O1Avi | 2.5055 |
C2A···H12A | 2.9117 | H14A···H12Biv | 2.5460 |
C2A···H10A | 2.7830 | H14B···C8Axiv | 3.0919 |
C2B···H10B | 2.9262 | H15A···O2Biv | 2.5476 |
C4A···H6A | 2.8266 | H15A···H12Biv | 2.5848 |
C4B···H10B | 2.9518 | H15B···O1Bii | 2.5855 |
C6A···H42A | 3.0023 | H15B···H1Bii | 2.4846 |
C6B···H1B | 2.8992 | H16A···C7Axv | 3.0572 |
C7A···H16Axii | 3.0572 | H16A···H7Axv | 2.5848 |
C7A···H12Aiii | 2.9214 | H16B···H31B | 2.5524 |
C8A···H14Bxiii | 3.0919 | H16B···C8Bviii | 2.9171 |
C8A···H32Aiii | 3.0205 | H16B···H8Bviii | 2.4737 |
C8B···H12A | 2.9929 | H31A···O1A | 2.8744 |
C8B···H16Bx | 2.9171 | H31A···C14Bvii | 2.7903 |
C10A···H2A | 2.9201 | H31A···C11A | 2.9921 |
C10B···H42B | 2.8265 | H31A···C13Bvii | 2.9377 |
C10B···H2B | 2.7962 | H31B···O1B | 2.8968 |
C11A···H31A | 2.9921 | H31B···H16B | 2.5524 |
C11B···H31B | 3.0554 | H31B···C11B | 3.0554 |
C12A···H2A | 2.9344 | H31B···C16B | 2.8626 |
C12A···H8B | 2.9014 | H32A···C8Aiii | 3.0205 |
C13B···H42Bix | 2.8816 | H41A···H1A | 2.2763 |
C13B···H31Axi | 2.9377 | H41A···O2Biii | 2.7923 |
C14B···H10Bix | 3.0776 | H41B···H1B | 2.3380 |
C14B···H31Axi | 2.7903 | H42A···C6A | 3.0023 |
C16B···H31B | 2.8626 | H42B···C10B | 2.8265 |
H1A···S1Biii | 3.0557 | H42B···H10B | 2.4835 |
H1A···H41A | 2.2763 | H42B···C13Bix | 2.8816 |
O2A—S1A—C2A | 105.92 (14) | C15A—C14A—H14A | 119.50 |
O2A—S1A—C11A | 107.38 (14) | C16A—C15A—H15A | 120.25 |
C2A—S1A—C11A | 96.60 (15) | C14A—C15A—H15A | 119.99 |
C2B—S1B—C11B | 96.69 (15) | C11A—C16A—H16A | 120.37 |
O2B—S1B—C11B | 106.72 (15) | C15A—C16A—H16A | 120.21 |
O2B—S1B—C2B | 104.73 (15) | O1B—C1B—C2B | 106.3 (2) |
C1A—O1A—H1A | 109.52 | C2B—C1B—C5B | 118.8 (3) |
C1B—O1B—H1B | 109.15 | O1B—C1B—C5B | 112.5 (3) |
C2A—C1A—C5A | 119.6 (3) | C4B—C1B—C5B | 117.8 (3) |
C2A—C1A—C4A | 87.0 (2) | S1B—C2B—C3B | 119.8 (2) |
O1A—C1A—C2A | 107.8 (2) | C1B—C2B—C3B | 88.7 (2) |
O1A—C1A—C5A | 110.1 (2) | S1B—C2B—C1B | 116.5 (2) |
O1A—C1A—C4A | 111.4 (2) | C2B—C3B—C4B | 88.4 (2) |
C4A—C1A—C5A | 118.9 (3) | C1B—C4B—C3B | 89.7 (2) |
S1A—C2A—C3A | 117.3 (2) | C1B—C5B—C6B | 121.2 (3) |
S1A—C2A—C1A | 118.1 (2) | C6B—C5B—C10B | 118.6 (4) |
C1A—C2A—C3A | 88.6 (2) | C1B—C5B—C10B | 120.1 (3) |
C2A—C3A—C4A | 88.3 (2) | C5B—C6B—C7B | 120.7 (5) |
C1A—C4A—C3A | 89.0 (2) | C6B—C7B—C8B | 119.7 (6) |
C1A—C5A—C6A | 119.1 (3) | C7B—C8B—C9B | 120.7 (6) |
C6A—C5A—C10A | 119.2 (3) | C8B—C9B—C10B | 119.6 (5) |
C1A—C5A—C10A | 121.6 (3) | C5B—C10B—C9B | 120.6 (5) |
C5A—C6A—C7A | 120.5 (4) | S1B—C11B—C12B | 121.3 (2) |
C6A—C7A—C8A | 119.9 (4) | C12B—C11B—C16B | 120.2 (3) |
C7A—C8A—C9A | 120.0 (4) | S1B—C11B—C16B | 118.6 (3) |
C8A—C9A—C10A | 120.0 (5) | C11B—C12B—C13B | 119.3 (3) |
C5A—C10A—C9A | 120.4 (4) | C12B—C13B—C14B | 120.7 (4) |
S1A—C11A—C12A | 121.3 (3) | C13B—C14B—C15B | 120.6 (4) |
C12A—C11A—C16A | 120.3 (3) | C14B—C15B—C16B | 119.9 (4) |
S1A—C11A—C16A | 118.4 (2) | C11B—C16B—C15B | 119.3 (4) |
C11A—C12A—C13A | 120.0 (3) | S1B—C2B—H2B | 109.99 |
C12A—C13A—C14A | 119.3 (3) | C1B—C2B—H2B | 110.13 |
C13A—C14A—C15A | 121.1 (3) | C3B—C2B—H2B | 110.04 |
C14A—C15A—C16A | 119.8 (3) | C2B—C3B—H31B | 114.45 |
C11A—C16A—C15A | 119.4 (3) | C2B—C3B—H32B | 114.44 |
C1A—C2A—H2A | 110.41 | C4B—C3B—H31B | 114.40 |
C3A—C2A—H2A | 110.36 | C4B—C3B—H32B | 114.42 |
S1A—C2A—H2A | 110.34 | H31B—C3B—H32B | 109.57 |
C4A—C3A—H32A | 114.56 | C1B—C4B—H41B | 114.15 |
C4A—C3A—H31A | 114.50 | C1B—C4B—H42B | 114.18 |
C2A—C3A—H31A | 114.42 | C3B—C4B—H41B | 114.07 |
H31A—C3A—H32A | 109.43 | C3B—C4B—H42B | 114.25 |
C2A—C3A—H32A | 114.49 | H41B—C4B—H42B | 109.46 |
C1A—C4A—H41A | 114.32 | C5B—C6B—H6B | 119.67 |
C1A—C4A—H42A | 114.38 | C7B—C6B—H6B | 119.61 |
C3A—C4A—H41A | 114.30 | C6B—C7B—H7B | 120.12 |
C3A—C4A—H42A | 114.30 | C8B—C7B—H7B | 120.14 |
H41A—C4A—H42A | 109.45 | C7B—C8B—H8B | 119.60 |
C7A—C6A—H6A | 119.75 | C9B—C8B—H8B | 119.69 |
C5A—C6A—H6A | 119.74 | C8B—C9B—H9B | 120.20 |
C6A—C7A—H7A | 119.96 | C10B—C9B—H9B | 120.19 |
C8A—C7A—H7A | 120.10 | C5B—C10B—H10B | 119.65 |
C7A—C8A—H8A | 120.02 | C9B—C10B—H10B | 119.77 |
C9A—C8A—H8A | 119.99 | C11B—C12B—H12B | 120.33 |
C10A—C9A—H9A | 119.98 | C13B—C12B—H12B | 120.38 |
C8A—C9A—H9A | 120.05 | C12B—C13B—H13B | 119.68 |
C9A—C10A—H10A | 119.73 | C14B—C13B—H13B | 119.63 |
C5A—C10A—H10A | 119.86 | C13B—C14B—H14B | 119.76 |
C11A—C12A—H12A | 119.96 | C15B—C14B—H14B | 119.65 |
C13A—C12A—H12A | 120.00 | C14B—C15B—H15B | 120.08 |
C12A—C13A—H13A | 120.35 | C16B—C15B—H15B | 120.04 |
C14A—C13A—H13A | 120.35 | C11B—C16B—H16B | 120.30 |
C13A—C14A—H14A | 119.35 | C15B—C16B—H16B | 120.37 |
O2A—S1A—C2A—C1A | 93.1 (3) | C16A—C11A—C12A—C13A | −0.7 (6) |
O2A—S1A—C2A—C3A | −162.8 (2) | C12A—C11A—C16A—C15A | 0.6 (6) |
C11A—S1A—C2A—C1A | −156.7 (2) | S1A—C11A—C16A—C15A | −178.6 (3) |
C11A—S1A—C2A—C3A | −52.6 (2) | S1A—C11A—C12A—C13A | 178.5 (3) |
O2A—S1A—C11A—C12A | 52.1 (3) | C11A—C12A—C13A—C14A | −0.1 (6) |
O2A—S1A—C11A—C16A | −128.7 (3) | C12A—C13A—C14A—C15A | 1.0 (6) |
C2A—S1A—C11A—C12A | −56.9 (3) | C13A—C14A—C15A—C16A | −1.2 (6) |
C2A—S1A—C11A—C16A | 122.3 (3) | C14A—C15A—C16A—C11A | 0.4 (6) |
O2B—S1B—C2B—C3B | −163.3 (2) | O1B—C1B—C2B—C3B | −93.1 (3) |
C2B—S1B—C11B—C12B | −89.6 (3) | C4B—C1B—C2B—S1B | 141.7 (2) |
O2B—S1B—C2B—C1B | 91.9 (2) | O1B—C1B—C2B—S1B | 29.9 (3) |
O2B—S1B—C11B—C12B | 18.0 (3) | C5B—C1B—C4B—C3B | −139.8 (3) |
O2B—S1B—C11B—C16B | −161.9 (3) | O1B—C1B—C5B—C6B | 7.0 (4) |
C11B—S1B—C2B—C3B | −54.0 (3) | O1B—C1B—C5B—C10B | −175.2 (3) |
C2B—S1B—C11B—C16B | 90.5 (3) | C2B—C1B—C5B—C6B | 131.9 (3) |
C11B—S1B—C2B—C1B | −158.8 (2) | C2B—C1B—C5B—C10B | −50.2 (4) |
C4A—C1A—C2A—S1A | 140.4 (2) | C4B—C1B—C5B—C6B | −125.2 (4) |
C4A—C1A—C2A—C3A | 19.9 (2) | C4B—C1B—C5B—C10B | 52.7 (4) |
O1A—C1A—C2A—C3A | −91.6 (3) | O1B—C1B—C4B—C3B | 87.7 (3) |
O1A—C1A—C2A—S1A | 28.9 (3) | C2B—C1B—C4B—C3B | −18.6 (2) |
C4A—C1A—C5A—C10A | 137.8 (3) | C5B—C1B—C2B—S1B | −98.0 (3) |
C4A—C1A—C5A—C6A | −45.6 (4) | C5B—C1B—C2B—C3B | 139.0 (3) |
O1A—C1A—C5A—C6A | 84.6 (3) | C4B—C1B—C2B—C3B | 18.7 (2) |
C5A—C1A—C4A—C3A | −142.4 (3) | C1B—C2B—C3B—C4B | −18.6 (2) |
C2A—C1A—C5A—C6A | −149.8 (3) | S1B—C2B—C3B—C4B | −138.7 (2) |
C2A—C1A—C5A—C10A | 33.6 (4) | C2B—C3B—C4B—C1B | 19.1 (2) |
O1A—C1A—C5A—C10A | −92.0 (3) | C1B—C5B—C6B—C7B | 177.5 (4) |
C2A—C1A—C4A—C3A | −19.9 (2) | C10B—C5B—C6B—C7B | −0.4 (6) |
C5A—C1A—C2A—S1A | −97.8 (3) | C1B—C5B—C10B—C9B | −177.4 (4) |
O1A—C1A—C4A—C3A | 88.0 (3) | C6B—C5B—C10B—C9B | 0.4 (6) |
C5A—C1A—C2A—C3A | 141.7 (3) | C5B—C6B—C7B—C8B | −0.2 (7) |
C1A—C2A—C3A—C4A | −20.1 (2) | C6B—C7B—C8B—C9B | 0.7 (8) |
S1A—C2A—C3A—C4A | −141.3 (2) | C7B—C8B—C9B—C10B | −0.6 (8) |
C2A—C3A—C4A—C1A | 20.2 (2) | C8B—C9B—C10B—C5B | 0.0 (7) |
C10A—C5A—C6A—C7A | −0.9 (5) | S1B—C11B—C12B—C13B | 178.8 (3) |
C1A—C5A—C10A—C9A | 177.4 (3) | S1B—C11B—C16B—C15B | −177.5 (3) |
C1A—C5A—C6A—C7A | −177.5 (3) | C12B—C11B—C16B—C15B | 2.6 (5) |
C6A—C5A—C10A—C9A | 0.8 (5) | C16B—C11B—C12B—C13B | −1.3 (5) |
C5A—C6A—C7A—C8A | 0.1 (6) | C11B—C12B—C13B—C14B | −0.7 (6) |
C6A—C7A—C8A—C9A | 0.8 (7) | C12B—C13B—C14B—C15B | 1.5 (7) |
C7A—C8A—C9A—C10A | −0.8 (7) | C13B—C14B—C15B—C16B | −0.1 (7) |
C8A—C9A—C10A—C5A | 0.0 (6) | C14B—C15B—C16B—C11B | −1.9 (6) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) x, −y+3/2, z−1/2; (v) x, −y+1/2, z−1/2; (vi) x, −y+3/2, z+1/2; (vii) −x+2, y+1/2, −z+3/2; (viii) −x+1, y−1/2, −z+3/2; (ix) −x+1, −y+1, −z+2; (x) −x+1, y+1/2, −z+3/2; (xi) −x+2, y−1/2, −z+3/2; (xii) −x+2, y−1/2, −z+1/2; (xiii) x, y, z−1; (xiv) x, y, z+1; (xv) −x+2, y+1/2, −z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O2Biii | 0.95 | 1.79 | 2.735 (3) | 172 |
O1B—H1B···S1Ai | 0.95 | 2.81 | 3.697 (2) | 153 |
O1B—H1B···O2Ai | 0.95 | 1.74 | 2.698 (3) | 173 |
C6B—H6B···O1B | 0.95 | 2.42 | 2.776 (6) | 102 |
C12B—H12B···O2B | 0.95 | 2.60 | 2.971 (4) | 104 |
C13A—H13A···O1Avi | 0.95 | 2.51 | 3.226 (4) | 133 |
C15A—H15A···O2Biv | 0.95 | 2.55 | 3.472 (5) | 164 |
C15B—H15B···O1Bii | 0.95 | 2.59 | 3.436 (6) | 149 |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) x, −y+3/2, z−1/2; (vi) x, −y+3/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C16H16O2S |
Mr | 272.36 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 295 |
a, b, c (Å) | 10.439 (2), 17.361 (3), 15.555 (2) |
β (°) | 92.74 (1) |
V (Å3) | 2815.8 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.50 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-7R diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6253, 4965, 2695 |
Rint | 0.044 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.047, 0.138, 1.00 |
No. of reflections | 4965 |
No. of parameters | 344 |
H-atom treatment | H-atom parameters not refined |
Δρmax, Δρmin (e Å−3) | 0.32, −0.28 |
Computer programs: MSC/AFC7 Diffractometer Control Software (Molecular Structure Corporation, 1999), MSC/AFC7 Diffractometer Control Software, TEXSAN for Windows (Molecular Structure Corporation, 2001), TEXSAN for Windows and SHELXL97 (Sheldrick, 1997), PLATON (Spek, 1980-2001) and ORTEP-3 (Farrugia, 1997), TEXSAN for Windows and PLATON (Spek, 2001).
S1A—O2A | 1.512 (2) | S1B—C2B | 1.800 (3) |
S1A—C2A | 1.802 (3) | S1B—C11B | 1.783 (3) |
S1A—C11A | 1.785 (3) | O1A—C1A | 1.429 (4) |
S1B—O2B | 1.508 (3) | O1B—C1B | 1.411 (4) |
O2A—S1A—C2A | 105.92 (14) | S1A—C2A—C3A | 117.3 (2) |
O2A—S1A—C11A | 107.38 (14) | S1A—C11A—C12A | 121.3 (3) |
C2A—S1A—C11A | 96.60 (15) | S1A—C11A—C16A | 118.4 (2) |
C2B—S1B—C11B | 96.69 (15) | O1B—C1B—C2B | 106.3 (2) |
O2B—S1B—C11B | 106.72 (15) | C2B—C1B—C5B | 118.8 (3) |
O2B—S1B—C2B | 104.73 (15) | S1B—C2B—C3B | 119.8 (2) |
O1A—C1A—C2A | 107.8 (2) | S1B—C2B—C1B | 116.5 (2) |
O1A—C1A—C5A | 110.1 (2) | S1B—C11B—C12B | 121.3 (2) |
C4A—C1A—C5A | 118.9 (3) | S1B—C11B—C16B | 118.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···O2Bi | 0.95 | 1.79 | 2.735 (3) | 172 |
O1B—H1B···O2Aii | 0.95 | 1.74 | 2.698 (3) | 173 |
Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) −x+1, −y+1, −z+1. |
We have recently shown that a novel cyclization reaction between the lithium enolates of simple ketones and phenyl vinyl sulfoxide provides a simple and convenient route to the preparation of a diverse array of fused carbocyclic ring systems bearing a bridgehead hydroxy group (Loughlin et al., 2002). In the current study, use of the lithium enolate of acetophenone generated the novel monocyclic compound (I). Noteworthy was the formation of (I) as the major cyclobutanol isomer and the novel monoalkylated product 1-phenyl-4-phenylsulfinylbutan-1-one, (II), in a 64:36 ratio from achiral acetophenone and phenyl vinyl sulfoxide, with less than five percent of other products observed.
Compound (I) crystallizes in space group P21/c with two molecules, a and b, in the asymmetric unit (Figs. 1a and 1 b). The two molecules are structural isomers with the phenyl groups approximately orthogonal to their corresponding partners. The structure of the cyclobutanol sulfinyl core [OS(C4H5)OH] of the two molecules is similar, with relative stereochemistry (1RSc,2RSc,RSs), together with their enantiomers. The bond lengths and angles for this core are similar to those reported for related systems (Loughlin et al., 2002). The cyclobutane rings are distorted from planarity, with C1—C2—C3—C4 - 20.1 (2)° (molecule a) and -18.6 (2)° (molecule b). The O1—C1—C2—S1 torsion angles are 28.9 (3)° (molecule a) and 29.9 (3)° (molecule b).
In the crystal lattice, each molecule forms O—H···O—S hydrogen bonds (Fig. 2) with enantiomers of its partner molecule, generating a hydrogen-bonded chain along the a axis. Interestingly, the molecules along this chain are also linked through edge-to-face C—H···π interactions between the C1 phenyl groups.