Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015069/wn6046sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015069/wn60463asup2.hkl |
CCDC reference: 175366
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.007 Å
- R factor = 0.037
- wR factor = 0.069
- Data-to-parameter ratio = 13.4
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level A:
DIFF_012 Alert A _diffrn_reflns_av_R_equivalents is missing R factor for symmetry-equivalent intensities. The following tests will not be performed RINTA
1 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
0 Alert Level C = Please check
A mixture of (1-iodoethanesulfonyl)benzene (1) (600 mg), 3,3-dimethylbut-1-ene (2) (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 (hexanes–ethyl acetate 93:7) yielding (3a) (280 mg, isomer anti, 2S4R and 2R4S) and (3 b) (350 mg, isomer syn, 2R4R and 2S4S). Isometric crystals of (3a) were grown from hexane solution at room temperature over the course of a few days (m.p. = 346–348 K), 1H NMR (500 MHz, CDCl3): δ = 1.10 (s, 9H), 1.26 (d, J = 7.1 Hz, 1H), 1.88 (ddd, J = 16.4, 12.0, 1.9 Hz, 1H), 2.53 (ddd, J = 16.4, 8.5, 1.9 Hz, 1H), 3.45 (m, 1H), 4.42 (dd, J = 12.0, 1.9 Hz, 1H), 7.57–7.61 (m, 2H), 7.68 (tt, J = 7.4, 1.3 Hz, 1H), 7.89–7.92 (m, 2H). 13C NMR (125 MHz, CDCl3): δ = 16.72, 28.26, 35.98, 37.53, 56.14, 61.21, 128.88, 129.21, 133.79, 137.64.
H atoms belonging to CH2 groups and aromatic H atoms were included in the final stages of refinement, using a riding model with one common Uiso value refined for each group. 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 methyl group. The H atoms at C3 and C5 (C—H groups) were refined freely, together with their individual Uiso values.
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.
Fig. 1. The molecular structure of (3a). Displacement ellipsoids are shown at the 50% probability level and H atoms are drawn with an arbitrary radius. |
C14H21IO2S | Dx = 1.578 Mg m−3 |
Mr = 380.27 | Melting point: 73-75 °C K |
Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ac 2ab | Cell parameters from 30 reflections |
a = 7.6427 (14) Å | θ = 7.7–13.8° |
b = 11.035 (2) Å | µ = 2.13 mm−1 |
c = 37.950 (5) Å | T = 293 K |
V = 3200.6 (10) Å3 | Isometric, colourless |
Z = 8 | 0.90 × 0.80 × 0.57 mm |
F(000) = 1520 |
Siemens P4 diffractometer | 1891 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | θmax = 25.0°, θmin = 2.2° |
Graphite monochromator | h = 0→9 |
ω scans | k = 0→13 |
Absorption correction: numerical (Stoe & Cie, 1996) | l = 0→45 |
Tmin = 0.215, Tmax = 0.362 | 3 standard reflections every 100 reflections |
2815 measured reflections | intensity decay: none |
2815 independent reflections |
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)] = 0.037 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.069 | w = 1/[σ2(Fo2) + (0.012P)2 + 9.P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max = 0.001 |
2815 reflections | Δρmax = 0.55 e Å−3 |
210 parameters | Δρmin = −0.55 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: 0.00258 (8) |
C14H21IO2S | V = 3200.6 (10) Å3 |
Mr = 380.27 | Z = 8 |
Orthorhombic, Pbca | Mo Kα radiation |
a = 7.6427 (14) Å | µ = 2.13 mm−1 |
b = 11.035 (2) Å | T = 293 K |
c = 37.950 (5) Å | 0.90 × 0.80 × 0.57 mm |
Siemens P4 diffractometer | 2815 independent reflections |
Absorption correction: numerical (Stoe & Cie, 1996) | 1891 reflections with I > 2σ(I) |
Tmin = 0.215, Tmax = 0.362 | 3 standard reflections every 100 reflections |
2815 measured reflections | intensity decay: none |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.069 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.01 | Δρmax = 0.55 e Å−3 |
2815 reflections | Δρmin = −0.55 e Å−3 |
210 parameters |
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 | 0.13696 (4) | 0.80390 (4) | 0.415289 (9) | 0.06613 (16) | |
S1 | −0.36916 (16) | 0.80333 (11) | 0.33542 (3) | 0.0464 (3) | |
O1 | −0.3582 (5) | 0.8880 (3) | 0.30673 (9) | 0.0660 (10) | |
O2 | −0.4507 (4) | 0.8429 (3) | 0.36774 (9) | 0.0624 (10) | |
C1 | −0.1398 (7) | 0.7158 (5) | 0.47958 (12) | 0.0696 (16) | |
H1a | −0.1793 | 0.6679 | 0.4991 | 0.072 (10)* | |
H1b | −0.2062 | 0.7895 | 0.4785 | 0.072 (10)* | |
H1c | −0.0181 | 0.7347 | 0.4826 | 0.072 (10)* | |
C2 | −0.1650 (7) | 0.6444 (5) | 0.44536 (12) | 0.0522 (13) | |
C3 | −0.1277 (6) | 0.7262 (4) | 0.41351 (12) | 0.0408 (10) | |
H3 | −0.188 (5) | 0.802 (4) | 0.4151 (11) | 0.053* | |
C4 | −0.1457 (6) | 0.6674 (4) | 0.37730 (11) | 0.0466 (12) | |
H41 | −0.2525 | 0.6199 | 0.3771 | 0.056 (9)* | |
H42 | −0.0488 | 0.6117 | 0.3741 | 0.056 (9)* | |
C5 | −0.1500 (6) | 0.7543 (4) | 0.34574 (11) | 0.0409 (11) | |
H5 | −0.099 (6) | 0.837 (4) | 0.3523 (11) | 0.053* | |
C6 | −0.0608 (6) | 0.7039 (5) | 0.31319 (12) | 0.0538 (13) | |
H61 | −0.0786 | 0.7582 | 0.2938 | 0.065 (9)* | |
H62 | −0.1097 | 0.6261 | 0.3076 | 0.065 (9)* | |
H63 | 0.0622 | 0.6955 | 0.3176 | 0.065 (9)* | |
C7 | −0.3595 (8) | 0.6085 (6) | 0.44328 (15) | 0.086 (2) | |
H71 | −0.3925 | 0.5669 | 0.4645 | 0.099 (12)* | |
H72 | −0.3775 | 0.5561 | 0.4234 | 0.099 (12)* | |
H73 | −0.4298 | 0.6800 | 0.4406 | 0.099 (12)* | |
C8 | −0.0521 (8) | 0.5313 (5) | 0.44581 (15) | 0.0769 (19) | |
H81 | −0.0822 | 0.4826 | 0.4659 | 0.093 (12)* | |
H82 | 0.0689 | 0.5540 | 0.4472 | 0.093 (12)* | |
H83 | −0.0717 | 0.4857 | 0.4246 | 0.093 (12)* | |
C11 | −0.4839 (6) | 0.6740 (4) | 0.31984 (12) | 0.0430 (12) | |
C12 | −0.4752 (7) | 0.6433 (5) | 0.28446 (12) | 0.0553 (14) | |
H12 | −0.4069 | 0.6885 | 0.2690 | 0.067 (7)* | |
C13 | −0.5689 (8) | 0.5454 (5) | 0.27249 (14) | 0.0687 (17) | |
H13 | −0.5623 | 0.5233 | 0.2489 | 0.067 (7)* | |
C14 | −0.6727 (7) | 0.4797 (5) | 0.29532 (16) | 0.0643 (16) | |
H14 | −0.7377 | 0.4146 | 0.2869 | 0.067 (7)* | |
C15 | −0.6805 (6) | 0.5098 (5) | 0.33030 (15) | 0.0594 (14) | |
H15 | −0.7495 | 0.4643 | 0.3456 | 0.067 (7)* | |
C16 | −0.5864 (6) | 0.6074 (5) | 0.34308 (13) | 0.0521 (13) | |
H16 | −0.5916 | 0.6282 | 0.3668 | 0.067 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
I1 | 0.0485 (2) | 0.0921 (3) | 0.0578 (2) | −0.0152 (2) | −0.00716 (18) | −0.0001 (2) |
S1 | 0.0485 (6) | 0.0403 (6) | 0.0503 (6) | 0.0081 (6) | −0.0082 (6) | −0.0003 (6) |
O1 | 0.076 (2) | 0.048 (2) | 0.074 (2) | 0.001 (2) | −0.019 (2) | 0.0213 (19) |
O2 | 0.058 (2) | 0.064 (2) | 0.065 (2) | 0.0155 (19) | −0.0026 (18) | −0.0211 (19) |
C1 | 0.077 (4) | 0.087 (4) | 0.045 (3) | 0.005 (4) | 0.008 (3) | 0.005 (3) |
C2 | 0.058 (3) | 0.058 (3) | 0.041 (3) | 0.000 (3) | −0.004 (2) | 0.007 (2) |
C3 | 0.039 (2) | 0.039 (3) | 0.045 (2) | −0.002 (2) | −0.007 (2) | 0.000 (2) |
C4 | 0.052 (3) | 0.042 (3) | 0.045 (3) | 0.005 (3) | −0.012 (2) | −0.001 (2) |
C5 | 0.042 (3) | 0.038 (2) | 0.043 (3) | 0.001 (2) | −0.006 (2) | −0.002 (2) |
C6 | 0.054 (3) | 0.060 (3) | 0.047 (3) | 0.010 (3) | 0.002 (2) | 0.002 (3) |
C7 | 0.076 (4) | 0.114 (5) | 0.068 (4) | −0.034 (4) | −0.001 (4) | 0.023 (4) |
C8 | 0.108 (5) | 0.064 (4) | 0.059 (4) | 0.011 (4) | −0.010 (4) | 0.014 (3) |
C11 | 0.040 (2) | 0.045 (3) | 0.044 (3) | 0.006 (2) | −0.007 (2) | 0.002 (2) |
C12 | 0.068 (3) | 0.065 (4) | 0.033 (3) | −0.006 (3) | −0.006 (2) | 0.006 (3) |
C13 | 0.085 (4) | 0.070 (4) | 0.050 (3) | 0.002 (4) | −0.022 (3) | −0.009 (3) |
C14 | 0.061 (4) | 0.050 (3) | 0.082 (4) | −0.001 (3) | −0.032 (3) | −0.009 (3) |
C15 | 0.047 (3) | 0.059 (3) | 0.072 (4) | −0.003 (3) | −0.010 (3) | 0.012 (3) |
C16 | 0.044 (3) | 0.065 (3) | 0.048 (3) | 0.005 (3) | −0.005 (2) | 0.002 (3) |
I1—C3 | 2.198 (4) | C6—H62 | 0.9600 |
S1—O1 | 1.437 (3) | C6—H63 | 0.9600 |
S1—O2 | 1.443 (3) | C7—H71 | 0.9600 |
S1—C11 | 1.776 (5) | C7—H72 | 0.9600 |
S1—C5 | 1.803 (5) | C7—H73 | 0.9600 |
C1—C2 | 1.531 (7) | C8—H81 | 0.9600 |
C1—H1a | 0.9600 | C8—H82 | 0.9600 |
C1—H1b | 0.9600 | C8—H83 | 0.9600 |
C1—H1c | 0.9600 | C11—C12 | 1.386 (6) |
C2—C3 | 1.535 (6) | C11—C16 | 1.389 (6) |
C2—C8 | 1.518 (7) | C12—C13 | 1.373 (7) |
C2—C7 | 1.541 (7) | C12—H12 | 0.9300 |
C3—C4 | 1.526 (6) | C13—C14 | 1.381 (8) |
C3—H3 | 0.96 (4) | C13—H13 | 0.9300 |
C4—C5 | 1.535 (6) | C14—C15 | 1.370 (7) |
C4—H41 | 0.9700 | C14—H14 | 0.9300 |
C4—H42 | 0.9700 | C15—C16 | 1.383 (7) |
C5—C6 | 1.516 (6) | C15—H15 | 0.9300 |
C5—H5 | 1.02 (4) | C16—H16 | 0.9300 |
C6—H61 | 0.9600 | ||
O1—S1—O2 | 118.2 (2) | C5—C6—H63 | 109.5 |
O1—S1—C11 | 107.4 (2) | H61—C6—H63 | 109.5 |
O2—S1—C11 | 108.2 (2) | H62—C6—H63 | 109.5 |
O1—S1—C5 | 107.8 (2) | C2—C7—H71 | 109.5 |
O2—S1—C5 | 107.9 (2) | C2—C7—H72 | 109.5 |
C11—S1—C5 | 106.9 (2) | H71—C7—H72 | 109.5 |
C1—C2—C3 | 110.0 (4) | C2—C7—H73 | 109.5 |
C1—C2—C8 | 110.0 (4) | H71—C7—H73 | 109.5 |
C3—C2—C8 | 112.8 (4) | H72—C7—H73 | 109.5 |
C1—C2—C7 | 107.3 (5) | C2—C8—H81 | 109.5 |
C3—C2—C7 | 106.9 (4) | C2—C8—H82 | 109.5 |
C8—C2—C7 | 109.7 (5) | H81—C8—H82 | 109.5 |
C4—C3—C2 | 116.3 (4) | C2—C8—H83 | 109.5 |
C4—C3—I1 | 106.1 (3) | H81—C8—H83 | 109.5 |
C2—C3—I1 | 112.1 (3) | H82—C8—H83 | 109.5 |
C4—C3—H3 | 113 (3) | C12—C11—C16 | 120.8 (5) |
C2—C3—H3 | 112 (3) | C12—C11—S1 | 119.7 (4) |
I1—C3—H3 | 96 (3) | C16—C11—S1 | 119.5 (4) |
C3—C4—C5 | 116.0 (4) | C13—C12—C11 | 119.2 (5) |
C3—C4—H41 | 108.3 | C13—C12—H12 | 120.4 |
C5—C4—H41 | 108.3 | C11—C12—H12 | 120.4 |
C3—C4—H42 | 108.3 | C14—C13—C12 | 120.4 (5) |
C5—C4—H42 | 108.3 | C14—C13—H13 | 119.8 |
H41—C4—H42 | 107.4 | C12—C13—H13 | 119.8 |
C6—C5—C4 | 113.4 (4) | C15—C14—C13 | 120.4 (5) |
C6—C5—S1 | 110.5 (3) | C15—C14—H14 | 119.8 |
C4—C5—S1 | 112.1 (3) | C13—C14—H14 | 119.8 |
C6—C5—H5 | 111 (3) | C14—C15—C16 | 120.4 (5) |
C4—C5—H5 | 111 (2) | C14—C15—H15 | 119.8 |
S1—C5—H5 | 98 (2) | C16—C15—H15 | 119.8 |
C5—C6—H61 | 109.5 | C15—C16—C11 | 118.8 (5) |
C5—C6—H62 | 109.5 | C15—C16—H16 | 120.6 |
H61—C6—H62 | 109.5 | C11—C16—H16 | 120.6 |
C1—C2—C3—C4 | 179.5 (4) | C11—S1—C5—C4 | −67.4 (4) |
C8—C2—C3—C4 | 56.3 (6) | O1—S1—C11—C12 | 28.9 (5) |
C7—C2—C3—C4 | −64.4 (6) | O2—S1—C11—C12 | 157.6 (4) |
C1—C2—C3—I1 | 57.2 (5) | C5—S1—C11—C12 | −86.5 (4) |
C8—C2—C3—I1 | −66.0 (5) | O1—S1—C11—C16 | −148.8 (4) |
C7—C2—C3—I1 | 173.4 (4) | O2—S1—C11—C16 | −20.1 (4) |
C2—C3—C4—C5 | 166.5 (4) | C5—S1—C11—C16 | 95.8 (4) |
I1—C3—C4—C5 | −68.1 (4) | C16—C11—C12—C13 | −0.3 (7) |
C3—C4—C5—C6 | 144.9 (4) | S1—C11—C12—C13 | −178.0 (4) |
C3—C4—C5—S1 | −89.1 (4) | C11—C12—C13—C14 | 1.1 (8) |
O1—S1—C5—C6 | −55.0 (4) | C12—C13—C14—C15 | −1.4 (8) |
O2—S1—C5—C6 | 176.4 (3) | C13—C14—C15—C16 | 0.9 (8) |
C11—S1—C5—C6 | 60.2 (4) | C14—C15—C16—C11 | −0.1 (7) |
O1—S1—C5—C4 | 177.4 (3) | C12—C11—C16—C15 | −0.2 (7) |
O2—S1—C5—C4 | 48.8 (4) | S1—C11—C16—C15 | 177.5 (4) |
Experimental details
Crystal data | |
Chemical formula | C14H21IO2S |
Mr | 380.27 |
Crystal system, space group | Orthorhombic, Pbca |
Temperature (K) | 293 |
a, b, c (Å) | 7.6427 (14), 11.035 (2), 37.950 (5) |
V (Å3) | 3200.6 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.13 |
Crystal size (mm) | 0.90 × 0.80 × 0.57 |
Data collection | |
Diffractometer | Siemens P4 diffractometer |
Absorption correction | Numerical (Stoe & Cie, 1996) |
Tmin, Tmax | 0.215, 0.362 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2815, 2815, 1891 |
Rint | ? |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.069, 1.01 |
No. of reflections | 2815 |
No. of parameters | 210 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.55, −0.55 |
Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXL97.
I1—C3 | 2.198 (4) | S1—C5 | 1.803 (5) |
S1—O1 | 1.437 (3) | C2—C3 | 1.535 (6) |
S1—O2 | 1.443 (3) | C3—C4 | 1.526 (6) |
S1—C11 | 1.776 (5) | ||
O1—S1—O2 | 118.2 (2) | C3—C2—C8 | 112.8 (4) |
O1—S1—C11 | 107.4 (2) | C3—C2—C7 | 106.9 (4) |
O2—S1—C11 | 108.2 (2) | C4—C3—C2 | 116.3 (4) |
O1—S1—C5 | 107.8 (2) | C4—C3—I1 | 106.1 (3) |
O2—S1—C5 | 107.9 (2) | C2—C3—I1 | 112.1 (3) |
C11—S1—C5 | 106.9 (2) | C3—C4—C5 | 116.0 (4) |
C1—C2—C3 | 110.0 (4) | ||
C1—C2—C3—C4 | 179.5 (4) | C7—C2—C3—I1 | 173.4 (4) |
C8—C2—C3—C4 | 56.3 (6) | C2—C3—C4—C5 | 166.5 (4) |
C7—C2—C3—C4 | −64.4 (6) | I1—C3—C4—C5 | −68.1 (4) |
C1—C2—C3—I1 | 57.2 (5) | C3—C4—C5—C6 | 144.9 (4) |
C8—C2—C3—I1 | −66.0 (5) |
In the course of our continuing study on atom-transfer free radical additions of α-iodoalkylphenyl sulfones to alkenes, we found secondary iodide (1) reacting with terminal alkene (2) under standard conditions (Jankowski et al., 1995; Masnyk, 1991), producing a chromatographically separable mixture of diastereomers (3a) and (3 b) in a 1:1.2 ratio. The correlation of the crystal structure with the corresponding NMR spectrum will enable the application of NMR techniques to stereochemical assignments of other related compounds resulting from analogous reactions. We now present the crystal structure of (3a) (Fig. 1).
The compound crystallizes in the centrosymmetric space group Pbca with one molecule in the asymmetric unit. All bond lengths, bond angles and torsion angles are in the expected ranges. This includes a significantly enlarged O—S—O angle of 118.2° for the S═O double bonds. The geometric deviations at atoms C3 and C4, as expressed by bond angles of 116.3 (4) and 116.0 (4)°, respectively, can be related to the steric effect of bulky groups attached to C3 (tert-butyl and iodine) and C4 [–CH(CH3) and –SO2(C6H5)] favouring a more stretched arrangement of the aliphatic part of the molecule.