Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015070/wn6047sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015070/wn60473bsup2.hkl |
CCDC reference: 175367
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.006 Å
- R factor = 0.035
- wR factor = 0.066
- Data-to-parameter ratio = 15.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
ABSTM_02 The ratio of expected to reported Tmax/Tmin(RR) is > 1.10 Tmin and Tmax reported: 0.459 0.623 Tmin and Tmax expected: 0.294 0.531 RR = 1.329 Please check that your absorption correction is appropriate. REFLT_03 From the CIF: _diffrn_reflns_theta_max 32.50 From the CIF: _reflns_number_total 3189 Count of symmetry unique reflns 3020 Completeness (_total/calc) 105.60% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 169 Fraction of Friedel pairs measured 0.056 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
A mixture of (1-iodoethanesulfonyl)benzene (600 mg), 3,3-dimethylbut-1-ene (1.0 ml), benzene (1.5 ml) and benzoyl peroxide (40 mg) was heated for 6 h at 373 K in a sealed tube. The reaction mixture was then chromatographed on silica gel (hexane–ethyl acetate 93:7) yielding 280 mg of the anti isomer (2S4R and 2R4S) and 350 mg of the syn isomer (2R4R and 2S4S) (m.p. = 369–371 K). 1H NMR (500 MHz, CDCl3): δ = 1.08 (s, 9H), 1.25 (d, J = 6.8 Hz, 3H), 1.76 (ddd, J = 14.5, 11.2, 2.1 Hz, 1H), 2.35 (ddd, J = 14.5, 12.3, 2.6 Hz, 1H), 3.43 (dqd, J = 11.2, 6.8, 2.6 Hz, 1H), 3.88 (dd, J = 12.3, 2.1 Hz, 1H), 7.57–7.61 (m, 2H), 7.68 (tt, J = 7.4, 1.2 Hz, 1H), 7.89–7.92 (m, 2H). 13C NMR (125 MHz, CDCl3): δ = 11.63, 28.49, 34.44, 35.90, 51.85, 61.00, 128.83, 129.17, 133.77, 137.29.
The needle-shaped crystal was mounted using a glass capillary aligned along the ϕ axis. This special orientation leads to maximal and minimal transmission factors – used for absorption correction – which are different from the theoretical values calulated from the crystal dimensions and the linear absorption coefficient. Atomic coordinates for all H atoms belonging to the CH2 and the CH groups were included in the final stages of refinement, using a riding model. H atoms belonging to methyl groups were included in the refinement riding on their attached C atom and allowed to rotate about the C—C bond with one common Uiso value refined for each group. The absolute configuration assignment has been checked following some generally accepted guidelines (Flack & Bernardinelli, 2000). A comparable refinement of the inverted structure yielded a Flack parameter – calculated by a `hole in one' method [n = 0.36 (2)] – indicating the wrong absolute structure assignment and significant higher R-values (wR2 = 0.0731 and R1 = 0.0377).
Data collection: XSCANS (Siemens, 1996); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXL97.
C14H21IO2S | F(000) = 380 |
Mr = 380.27 | Dx = 1.566 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 38 reflections |
a = 6.1329 (8) Å | θ = 7.0–12.5° |
b = 14.3524 (13) Å | µ = 2.11 mm−1 |
c = 9.4381 (10) Å | T = 293 K |
β = 103.919 (9)° | Needle, colourless |
V = 806.36 (15) Å3 | 1.00 × 0.50 × 0.30 mm |
Z = 2 |
Siemens P4 diffractometer | 2659 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 32.5°, θmin = 2.2° |
ω scans | h = −1→9 |
Absorption correction: numerical (Stoe & Cie, 1996) | k = −1→21 |
Tmin = 0.459, Tmax = 0.623 | l = −14→14 |
3964 measured reflections | 3 standard reflections every 100 reflections |
3189 independent reflections | intensity decay: none |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.035 | w = 1/[σ2(Fo2) + (0.01P)2 + 0.6P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.066 | (Δ/σ)max = 0.001 |
S = 1.07 | Δρmax = 0.93 e Å−3 |
3189 reflections | Δρmin = −0.73 e Å−3 |
207 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0178 (10) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983) |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.01 (2) |
C14H21IO2S | V = 806.36 (15) Å3 |
Mr = 380.27 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 6.1329 (8) Å | µ = 2.11 mm−1 |
b = 14.3524 (13) Å | T = 293 K |
c = 9.4381 (10) Å | 1.00 × 0.50 × 0.30 mm |
β = 103.919 (9)° |
Siemens P4 diffractometer | 2659 reflections with I > 2σ(I) |
Absorption correction: numerical (Stoe & Cie, 1996) | Rint = 0.012 |
Tmin = 0.459, Tmax = 0.623 | 3 standard reflections every 100 reflections |
3964 measured reflections | intensity decay: none |
3189 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.066 | Δρmax = 0.93 e Å−3 |
S = 1.07 | Δρmin = −0.73 e Å−3 |
3189 reflections | Absolute structure: Flack (1983) |
207 parameters | Absolute structure parameter: 0.01 (2) |
1 restraint |
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 | ||
I1 | 0.68297 (7) | 0.16370 (3) | 0.58303 (3) | 0.07695 (15) | |
S1 | 0.62742 (15) | 0.26294 (6) | 0.06758 (9) | 0.03794 (17) | |
O1 | 0.3890 (4) | 0.2680 (2) | 0.0551 (3) | 0.0557 (7) | |
O2 | 0.7096 (5) | 0.2123 (2) | −0.0390 (3) | 0.0555 (7) | |
C1 | 0.7543 (10) | −0.0699 (4) | 0.5614 (5) | 0.0691 (15) | |
H1A | 0.7228 | −0.0343 | 0.6403 | 0.071 (10)* | |
H1B | 0.9133 | −0.0705 | 0.5694 | 0.071 (10)* | |
H1C | 0.7017 | −0.1326 | 0.5657 | 0.071 (10)* | |
C2 | 0.6344 (7) | −0.0256 (3) | 0.4157 (4) | 0.0472 (9) | |
C3 | 0.7295 (6) | 0.0736 (3) | 0.4052 (4) | 0.0392 (7) | |
H3 | 0.8918 | 0.0668 | 0.4169 | 0.047* | |
C4 | 0.6395 (6) | 0.1237 (3) | 0.2609 (4) | 0.0405 (8) | |
H4A | 0.4805 | 0.1356 | 0.2497 | 0.047 (12)* | |
H4B | 0.6546 | 0.0828 | 0.1821 | 0.038 (10)* | |
C5 | 0.7566 (6) | 0.2161 (3) | 0.2457 (4) | 0.0377 (7) | |
H5 | 0.7298 | 0.2594 | 0.3200 | 0.045* | |
C6 | 1.0088 (6) | 0.2072 (3) | 0.2628 (5) | 0.0503 (9) | |
H6A | 1.0684 | 0.2659 | 0.2409 | 0.073 (9)* | |
H6B | 1.0380 | 0.1605 | 0.1969 | 0.073 (9)* | |
H6C | 1.0792 | 0.1896 | 0.3613 | 0.073 (9)* | |
C7 | 0.3820 (9) | −0.0268 (5) | 0.3990 (7) | 0.0799 (18) | |
H7A | 0.3462 | 0.0064 | 0.4787 | 0.088 (12)* | |
H7B | 0.3313 | −0.0900 | 0.3991 | 0.088 (12)* | |
H7C | 0.3090 | 0.0025 | 0.3086 | 0.088 (12)* | |
C8 | 0.6918 (11) | −0.0842 (3) | 0.2949 (6) | 0.0687 (14) | |
H8A | 0.6111 | −0.0609 | 0.2016 | 0.092 (12)* | |
H8B | 0.6502 | −0.1478 | 0.3053 | 0.092 (12)* | |
H8C | 0.8503 | −0.0806 | 0.3017 | 0.092 (12)* | |
C11 | 0.7302 (6) | 0.3786 (2) | 0.0743 (4) | 0.0357 (7) | |
C12 | 0.9139 (7) | 0.3995 (3) | 0.0189 (4) | 0.0456 (9) | |
H12 | 0.9874 | 0.3531 | −0.0205 | 0.055* | |
C13 | 0.9862 (8) | 0.4920 (4) | 0.0236 (5) | 0.0568 (11) | |
H13 | 1.1103 | 0.5073 | −0.0122 | 0.068* | |
C14 | 0.8769 (8) | 0.5601 (3) | 0.0800 (5) | 0.0593 (11) | |
H14 | 0.9261 | 0.6215 | 0.0816 | 0.071* | |
C15 | 0.6950 (9) | 0.5385 (3) | 0.1342 (5) | 0.0601 (12) | |
H15 | 0.6219 | 0.5855 | 0.1726 | 0.072* | |
C16 | 0.6187 (7) | 0.4475 (3) | 0.1324 (5) | 0.0465 (9) | |
H16 | 0.4954 | 0.4329 | 0.1693 | 0.056* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.1274 (3) | 0.06195 (19) | 0.04630 (14) | 0.0108 (3) | 0.03034 (15) | −0.0021 (2) |
S1 | 0.0380 (4) | 0.0373 (4) | 0.0375 (4) | −0.0001 (4) | 0.0072 (3) | 0.0053 (4) |
O1 | 0.0376 (13) | 0.0593 (18) | 0.0662 (17) | −0.0024 (15) | 0.0047 (12) | 0.0180 (16) |
O2 | 0.0748 (19) | 0.0484 (16) | 0.0430 (13) | −0.0028 (15) | 0.0137 (13) | −0.0072 (12) |
C1 | 0.091 (4) | 0.058 (3) | 0.053 (2) | 0.003 (3) | 0.007 (3) | 0.022 (2) |
C2 | 0.050 (2) | 0.041 (2) | 0.048 (2) | −0.0020 (17) | 0.0056 (17) | 0.0124 (17) |
C3 | 0.0422 (18) | 0.0377 (17) | 0.0376 (15) | 0.0031 (15) | 0.0093 (14) | 0.0061 (14) |
C4 | 0.0390 (18) | 0.0428 (19) | 0.0376 (16) | −0.0019 (16) | 0.0052 (14) | 0.0067 (15) |
C5 | 0.0399 (17) | 0.0356 (17) | 0.0359 (15) | 0.0020 (15) | 0.0059 (13) | 0.0024 (13) |
C6 | 0.0417 (19) | 0.044 (2) | 0.061 (2) | −0.0035 (17) | 0.0032 (17) | 0.0078 (19) |
C7 | 0.056 (3) | 0.073 (4) | 0.107 (5) | −0.010 (3) | 0.013 (3) | 0.031 (4) |
C8 | 0.102 (4) | 0.041 (2) | 0.061 (3) | −0.006 (3) | 0.015 (3) | 0.000 (2) |
C11 | 0.0361 (17) | 0.0337 (16) | 0.0377 (16) | 0.0041 (14) | 0.0093 (14) | 0.0079 (13) |
C12 | 0.044 (2) | 0.048 (2) | 0.048 (2) | 0.0043 (17) | 0.0152 (17) | 0.0092 (17) |
C13 | 0.046 (2) | 0.061 (3) | 0.065 (3) | −0.007 (2) | 0.016 (2) | 0.021 (2) |
C14 | 0.069 (3) | 0.041 (2) | 0.061 (2) | −0.007 (2) | 0.001 (2) | 0.014 (2) |
C15 | 0.080 (3) | 0.040 (2) | 0.059 (2) | 0.014 (2) | 0.015 (2) | 0.0013 (19) |
C16 | 0.050 (2) | 0.042 (2) | 0.052 (2) | 0.0093 (17) | 0.0215 (18) | 0.0054 (17) |
I1—C3 | 2.191 (4) | C6—H6B | 0.9600 |
S1—O2 | 1.428 (3) | C6—H6C | 0.9600 |
S1—O1 | 1.440 (3) | C7—H7A | 0.9600 |
S1—C11 | 1.771 (4) | C7—H7B | 0.9600 |
S1—C5 | 1.807 (3) | C7—H7C | 0.9600 |
C1—C2 | 1.532 (6) | C8—H8A | 0.9600 |
C1—H1A | 0.9600 | C8—H8B | 0.9600 |
C1—H1B | 0.9600 | C8—H8C | 0.9600 |
C1—H1C | 0.9600 | C11—C12 | 1.385 (5) |
C2—C8 | 1.525 (7) | C11—C16 | 1.388 (5) |
C2—C7 | 1.518 (6) | C12—C13 | 1.397 (6) |
C2—C3 | 1.551 (5) | C12—H12 | 0.9300 |
C3—C4 | 1.521 (5) | C13—C14 | 1.364 (7) |
C3—H3 | 0.9800 | C13—H13 | 0.9300 |
C4—C5 | 1.531 (5) | C14—C15 | 1.370 (7) |
C4—H4A | 0.9700 | C14—H14 | 0.9300 |
C4—H4B | 0.9700 | C15—C16 | 1.386 (6) |
C5—C6 | 1.522 (5) | C15—H15 | 0.9300 |
C5—H5 | 0.9800 | C16—H16 | 0.9300 |
C6—H6A | 0.9600 | ||
O2—S1—O1 | 119.43 (19) | C6—C5—S1 | 109.7 (3) |
O2—S1—C11 | 108.65 (17) | C4—C5—S1 | 107.4 (2) |
O1—S1—C11 | 107.54 (18) | C6—C5—H5 | 108.6 |
O2—S1—C5 | 108.44 (18) | C4—C5—H5 | 108.6 |
O1—S1—C5 | 107.69 (17) | S1—C5—H5 | 108.6 |
C11—S1—C5 | 104.03 (17) | C5—C6—H6A | 109.5 |
C2—C1—H1A | 109.5 | C5—C6—H6B | 109.5 |
C2—C1—H1B | 109.5 | H6A—C6—H6B | 109.5 |
H1A—C1—H1B | 109.5 | C5—C6—H6C | 109.5 |
C2—C1—H1C | 109.5 | H6A—C6—H6C | 109.5 |
H1A—C1—H1C | 109.5 | H6B—C6—H6C | 109.5 |
H1B—C1—H1C | 109.5 | C2—C7—H7A | 109.5 |
C8—C2—C7 | 109.2 (4) | C2—C7—H7B | 109.5 |
C8—C2—C1 | 107.2 (4) | H7A—C7—H7B | 109.5 |
C7—C2—C1 | 110.2 (4) | C2—C7—H7C | 109.5 |
C8—C2—C3 | 107.5 (3) | H7A—C7—H7C | 109.5 |
C7—C2—C3 | 113.2 (4) | H7B—C7—H7C | 109.5 |
C1—C2—C3 | 109.4 (4) | C2—C8—H8A | 109.5 |
C4—C3—C2 | 115.5 (3) | C2—C8—H8B | 109.5 |
C4—C3—I1 | 108.7 (2) | H8A—C8—H8B | 109.5 |
C2—C3—I1 | 111.9 (2) | C2—C8—H8C | 109.5 |
C4—C3—H3 | 106.8 | H8A—C8—H8C | 109.5 |
C2—C3—H3 | 106.8 | H8B—C8—H8C | 109.5 |
I1—C3—H3 | 106.8 | C12—C11—C16 | 121.2 (4) |
C3—C4—C5 | 114.6 (3) | C12—C11—S1 | 120.3 (3) |
C3—C4—H4A | 108.6 | C16—C11—S1 | 118.5 (3) |
C5—C4—H4A | 108.6 | C11—C12—C13 | 118.3 (4) |
C3—C4—H4B | 108.6 | C14—C13—C12 | 120.8 (4) |
C5—C4—H4B | 108.6 | C13—C14—C15 | 120.3 (4) |
H4A—C4—H4B | 107.6 | C14—C15—C16 | 120.8 (4) |
C6—C5—C4 | 113.9 (3) | C11—C16—C15 | 118.7 (4) |
C8—C2—C3—C4 | 59.4 (5) | C11—S1—C5—C4 | 168.3 (2) |
C7—C2—C3—C4 | −61.3 (5) | O2—S1—C11—C12 | −18.8 (4) |
C1—C2—C3—C4 | 175.4 (4) | O1—S1—C11—C12 | −149.4 (3) |
C8—C2—C3—I1 | −175.6 (3) | C5—S1—C11—C12 | 96.5 (3) |
C7—C2—C3—I1 | 63.7 (4) | O2—S1—C11—C16 | 159.4 (3) |
C1—C2—C3—I1 | −59.6 (4) | O1—S1—C11—C16 | 28.8 (3) |
C2—C3—C4—C5 | −172.7 (3) | C5—S1—C11—C16 | −85.2 (3) |
I1—C3—C4—C5 | 60.6 (3) | C16—C11—C12—C13 | 0.4 (6) |
C3—C4—C5—C6 | 57.8 (4) | S1—C11—C12—C13 | 178.6 (3) |
C3—C4—C5—S1 | 179.4 (3) | C11—C12—C13—C14 | −0.7 (7) |
O2—S1—C5—C6 | 48.1 (3) | C12—C13—C14—C15 | 0.5 (7) |
O1—S1—C5—C6 | 178.6 (3) | C13—C14—C15—C16 | −0.2 (7) |
C11—S1—C5—C6 | −67.4 (3) | C12—C11—C16—C15 | −0.1 (6) |
O2—S1—C5—C4 | −76.2 (3) | S1—C11—C16—C15 | −178.3 (3) |
O1—S1—C5—C4 | 54.4 (3) | C14—C15—C16—C11 | −0.1 (7) |
Experimental details
Crystal data | |
Chemical formula | C14H21IO2S |
Mr | 380.27 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 6.1329 (8), 14.3524 (13), 9.4381 (10) |
β (°) | 103.919 (9) |
V (Å3) | 806.36 (15) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 2.11 |
Crystal size (mm) | 1.00 × 0.50 × 0.30 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Numerical (Stoe & Cie, 1996) |
Tmin, Tmax | 0.459, 0.623 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3964, 3189, 2659 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.756 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.066, 1.07 |
No. of reflections | 3189 |
No. of parameters | 207 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.93, −0.73 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.01 (2) |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXL97.
I1—C3 | 2.191 (4) | C2—C7 | 1.518 (6) |
S1—O2 | 1.428 (3) | C2—C3 | 1.551 (5) |
S1—O1 | 1.440 (3) | C3—C4 | 1.521 (5) |
S1—C11 | 1.771 (4) | C4—C5 | 1.531 (5) |
S1—C5 | 1.807 (3) | C5—C6 | 1.522 (5) |
C2—C8 | 1.525 (7) | ||
O2—S1—O1 | 119.43 (19) | C11—S1—C5 | 104.03 (17) |
O2—S1—C11 | 108.65 (17) | C4—C3—C2 | 115.5 (3) |
O1—S1—C11 | 107.54 (18) | C4—C3—I1 | 108.7 (2) |
O2—S1—C5 | 108.44 (18) | C2—C3—I1 | 111.9 (2) |
O1—S1—C5 | 107.69 (17) | C3—C4—C5 | 114.6 (3) |
C1—C2—C3—C4 | 175.4 (4) | C3—C4—C5—S1 | 179.4 (3) |
C2—C3—C4—C5 | −172.7 (3) | C11—S1—C5—C4 | 168.3 (2) |
As we have reported (Rei\&s & Masnyk, 2001), (1-iodoethanesulfonyl)benzene reacts with 3,3-dimethylbut-1-ene under standard conditions (Jankowski et al., 1995; Masnyk, 1991) to yield the chromatographically separable mixture of the RS,SR and the RR,SS diastereomers of (4-iodo-5,5-dimethyl-2-hexylsulfonyl)benzene. In this context, the crystal structure determination of the title compound, (3 b), was undertaken to relate the molecular structure to the 1H and 13C NMR data. This should allow us to predict the stereochemistry of analogous compounds from NMR data.
Crystallization of the title compond from hexane yielded needle-shaped colourless crystals. The compound crystallizes in the polar space group P21. The crystal is composed of molecules having a 2R,4R-configuration at both chiral atoms C3 and C5 (Fig. 1).
All bond lengths, bond angles and torsion angles are as expected, including a significant distortion from tetrahedral geometry at the S atom caused by the S═O double bonds (Table 1). Deviations of the ideal bond angles also occur at atoms C3 and C4 since the bulky substituents tert-butyl and iodine cause a stretching of the aliphatic section of the molecule. A reason for the formation of enantiopure crystals from a racemic solution of the title compound may be that the molecules do have an excellent fit within the bc plane (Fig. 2). This arrangement shows separated hydrophobic regions in the a0c and a1/2c planes as well as hydrophilic regions perpendicular to the bc plane (shaded cirles).