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Structure refinement of X-ray diffraction data in the polar space group P21 and the assignment of the absolute structure identified the crystal of the title compound, C14H21IO2S, under investigation as the 2R,4R isomer. The packing is dominated by hydro­phobic layers in the a0c and a½c planes and hydro­philic stacks along [100].

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801015070/wn6047sup1.cif
Contains datablocks 3b, diaster2

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801015070/wn60473bsup2.hkl
Contains datablock 3b

CCDC reference: 175367

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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

Comment top

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 SO 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).

Experimental top

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.

Refinement top

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).

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are shown at the 50% probability level and H atoms are drawn with an arbitrary radius.
[Figure 2] Fig. 2. The packing of the title compound viewed down [100].
(2R,4R)-(4-Iodo-5,5-dimethyl-2-hexylsulfonyl)benzene top
Crystal data top
C14H21IO2SF(000) = 380
Mr = 380.27Dx = 1.566 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 38 reflections
a = 6.1329 (8) Åθ = 7.0–12.5°
b = 14.3524 (13) ŵ = 2.11 mm1
c = 9.4381 (10) ÅT = 293 K
β = 103.919 (9)°Needle, colourless
V = 806.36 (15) Å31.00 × 0.50 × 0.30 mm
Z = 2
Data collection top
Siemens P4
diffractometer
2659 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.012
Graphite monochromatorθmax = 32.5°, θmin = 2.2°
ω scansh = 19
Absorption correction: numerical
(Stoe & Cie, 1996)
k = 121
Tmin = 0.459, Tmax = 0.623l = 1414
3964 measured reflections3 standard reflections every 100 reflections
3189 independent reflections intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH 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 = 1.07Δρmax = 0.93 e Å3
3189 reflectionsΔρmin = 0.73 e Å3
207 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraintExtinction coefficient: 0.0178 (10)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983)
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.01 (2)
Crystal data top
C14H21IO2SV = 806.36 (15) Å3
Mr = 380.27Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.1329 (8) ŵ = 2.11 mm1
b = 14.3524 (13) ÅT = 293 K
c = 9.4381 (10) Å1.00 × 0.50 × 0.30 mm
β = 103.919 (9)°
Data collection top
Siemens P4
diffractometer
2659 reflections with I > 2σ(I)
Absorption correction: numerical
(Stoe & Cie, 1996)
Rint = 0.012
Tmin = 0.459, Tmax = 0.6233 standard reflections every 100 reflections
3964 measured reflections intensity decay: none
3189 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.066Δρmax = 0.93 e Å3
S = 1.07Δρmin = 0.73 e Å3
3189 reflectionsAbsolute structure: Flack (1983)
207 parametersAbsolute structure parameter: 0.01 (2)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
I10.68297 (7)0.16370 (3)0.58303 (3)0.07695 (15)
S10.62742 (15)0.26294 (6)0.06758 (9)0.03794 (17)
O10.3890 (4)0.2680 (2)0.0551 (3)0.0557 (7)
O20.7096 (5)0.2123 (2)0.0390 (3)0.0555 (7)
C10.7543 (10)0.0699 (4)0.5614 (5)0.0691 (15)
H1A0.72280.03430.64030.071 (10)*
H1B0.91330.07050.56940.071 (10)*
H1C0.70170.13260.56570.071 (10)*
C20.6344 (7)0.0256 (3)0.4157 (4)0.0472 (9)
C30.7295 (6)0.0736 (3)0.4052 (4)0.0392 (7)
H30.89180.06680.41690.047*
C40.6395 (6)0.1237 (3)0.2609 (4)0.0405 (8)
H4A0.48050.13560.24970.047 (12)*
H4B0.65460.08280.18210.038 (10)*
C50.7566 (6)0.2161 (3)0.2457 (4)0.0377 (7)
H50.72980.25940.32000.045*
C61.0088 (6)0.2072 (3)0.2628 (5)0.0503 (9)
H6A1.06840.26590.24090.073 (9)*
H6B1.03800.16050.19690.073 (9)*
H6C1.07920.18960.36130.073 (9)*
C70.3820 (9)0.0268 (5)0.3990 (7)0.0799 (18)
H7A0.34620.00640.47870.088 (12)*
H7B0.33130.09000.39910.088 (12)*
H7C0.30900.00250.30860.088 (12)*
C80.6918 (11)0.0842 (3)0.2949 (6)0.0687 (14)
H8A0.61110.06090.20160.092 (12)*
H8B0.65020.14780.30530.092 (12)*
H8C0.85030.08060.30170.092 (12)*
C110.7302 (6)0.3786 (2)0.0743 (4)0.0357 (7)
C120.9139 (7)0.3995 (3)0.0189 (4)0.0456 (9)
H120.98740.35310.02050.055*
C130.9862 (8)0.4920 (4)0.0236 (5)0.0568 (11)
H131.11030.50730.01220.068*
C140.8769 (8)0.5601 (3)0.0800 (5)0.0593 (11)
H140.92610.62150.08160.071*
C150.6950 (9)0.5385 (3)0.1342 (5)0.0601 (12)
H150.62190.58550.17260.072*
C160.6187 (7)0.4475 (3)0.1324 (5)0.0465 (9)
H160.49540.43290.16930.056*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
I10.1274 (3)0.06195 (19)0.04630 (14)0.0108 (3)0.03034 (15)0.0021 (2)
S10.0380 (4)0.0373 (4)0.0375 (4)0.0001 (4)0.0072 (3)0.0053 (4)
O10.0376 (13)0.0593 (18)0.0662 (17)0.0024 (15)0.0047 (12)0.0180 (16)
O20.0748 (19)0.0484 (16)0.0430 (13)0.0028 (15)0.0137 (13)0.0072 (12)
C10.091 (4)0.058 (3)0.053 (2)0.003 (3)0.007 (3)0.022 (2)
C20.050 (2)0.041 (2)0.048 (2)0.0020 (17)0.0056 (17)0.0124 (17)
C30.0422 (18)0.0377 (17)0.0376 (15)0.0031 (15)0.0093 (14)0.0061 (14)
C40.0390 (18)0.0428 (19)0.0376 (16)0.0019 (16)0.0052 (14)0.0067 (15)
C50.0399 (17)0.0356 (17)0.0359 (15)0.0020 (15)0.0059 (13)0.0024 (13)
C60.0417 (19)0.044 (2)0.061 (2)0.0035 (17)0.0032 (17)0.0078 (19)
C70.056 (3)0.073 (4)0.107 (5)0.010 (3)0.013 (3)0.031 (4)
C80.102 (4)0.041 (2)0.061 (3)0.006 (3)0.015 (3)0.000 (2)
C110.0361 (17)0.0337 (16)0.0377 (16)0.0041 (14)0.0093 (14)0.0079 (13)
C120.044 (2)0.048 (2)0.048 (2)0.0043 (17)0.0152 (17)0.0092 (17)
C130.046 (2)0.061 (3)0.065 (3)0.007 (2)0.016 (2)0.021 (2)
C140.069 (3)0.041 (2)0.061 (2)0.007 (2)0.001 (2)0.014 (2)
C150.080 (3)0.040 (2)0.059 (2)0.014 (2)0.015 (2)0.0013 (19)
C160.050 (2)0.042 (2)0.052 (2)0.0093 (17)0.0215 (18)0.0054 (17)
Geometric parameters (Å, º) top
I1—C32.191 (4)C6—H6B0.9600
S1—O21.428 (3)C6—H6C0.9600
S1—O11.440 (3)C7—H7A0.9600
S1—C111.771 (4)C7—H7B0.9600
S1—C51.807 (3)C7—H7C0.9600
C1—C21.532 (6)C8—H8A0.9600
C1—H1A0.9600C8—H8B0.9600
C1—H1B0.9600C8—H8C0.9600
C1—H1C0.9600C11—C121.385 (5)
C2—C81.525 (7)C11—C161.388 (5)
C2—C71.518 (6)C12—C131.397 (6)
C2—C31.551 (5)C12—H120.9300
C3—C41.521 (5)C13—C141.364 (7)
C3—H30.9800C13—H130.9300
C4—C51.531 (5)C14—C151.370 (7)
C4—H4A0.9700C14—H140.9300
C4—H4B0.9700C15—C161.386 (6)
C5—C61.522 (5)C15—H150.9300
C5—H50.9800C16—H160.9300
C6—H6A0.9600
O2—S1—O1119.43 (19)C6—C5—S1109.7 (3)
O2—S1—C11108.65 (17)C4—C5—S1107.4 (2)
O1—S1—C11107.54 (18)C6—C5—H5108.6
O2—S1—C5108.44 (18)C4—C5—H5108.6
O1—S1—C5107.69 (17)S1—C5—H5108.6
C11—S1—C5104.03 (17)C5—C6—H6A109.5
C2—C1—H1A109.5C5—C6—H6B109.5
C2—C1—H1B109.5H6A—C6—H6B109.5
H1A—C1—H1B109.5C5—C6—H6C109.5
C2—C1—H1C109.5H6A—C6—H6C109.5
H1A—C1—H1C109.5H6B—C6—H6C109.5
H1B—C1—H1C109.5C2—C7—H7A109.5
C8—C2—C7109.2 (4)C2—C7—H7B109.5
C8—C2—C1107.2 (4)H7A—C7—H7B109.5
C7—C2—C1110.2 (4)C2—C7—H7C109.5
C8—C2—C3107.5 (3)H7A—C7—H7C109.5
C7—C2—C3113.2 (4)H7B—C7—H7C109.5
C1—C2—C3109.4 (4)C2—C8—H8A109.5
C4—C3—C2115.5 (3)C2—C8—H8B109.5
C4—C3—I1108.7 (2)H8A—C8—H8B109.5
C2—C3—I1111.9 (2)C2—C8—H8C109.5
C4—C3—H3106.8H8A—C8—H8C109.5
C2—C3—H3106.8H8B—C8—H8C109.5
I1—C3—H3106.8C12—C11—C16121.2 (4)
C3—C4—C5114.6 (3)C12—C11—S1120.3 (3)
C3—C4—H4A108.6C16—C11—S1118.5 (3)
C5—C4—H4A108.6C11—C12—C13118.3 (4)
C3—C4—H4B108.6C14—C13—C12120.8 (4)
C5—C4—H4B108.6C13—C14—C15120.3 (4)
H4A—C4—H4B107.6C14—C15—C16120.8 (4)
C6—C5—C4113.9 (3)C11—C16—C15118.7 (4)
C8—C2—C3—C459.4 (5)C11—S1—C5—C4168.3 (2)
C7—C2—C3—C461.3 (5)O2—S1—C11—C1218.8 (4)
C1—C2—C3—C4175.4 (4)O1—S1—C11—C12149.4 (3)
C8—C2—C3—I1175.6 (3)C5—S1—C11—C1296.5 (3)
C7—C2—C3—I163.7 (4)O2—S1—C11—C16159.4 (3)
C1—C2—C3—I159.6 (4)O1—S1—C11—C1628.8 (3)
C2—C3—C4—C5172.7 (3)C5—S1—C11—C1685.2 (3)
I1—C3—C4—C560.6 (3)C16—C11—C12—C130.4 (6)
C3—C4—C5—C657.8 (4)S1—C11—C12—C13178.6 (3)
C3—C4—C5—S1179.4 (3)C11—C12—C13—C140.7 (7)
O2—S1—C5—C648.1 (3)C12—C13—C14—C150.5 (7)
O1—S1—C5—C6178.6 (3)C13—C14—C15—C160.2 (7)
C11—S1—C5—C667.4 (3)C12—C11—C16—C150.1 (6)
O2—S1—C5—C476.2 (3)S1—C11—C16—C15178.3 (3)
O1—S1—C5—C454.4 (3)C14—C15—C16—C110.1 (7)

Experimental details

Crystal data
Chemical formulaC14H21IO2S
Mr380.27
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)6.1329 (8), 14.3524 (13), 9.4381 (10)
β (°) 103.919 (9)
V3)806.36 (15)
Z2
Radiation typeMo Kα
µ (mm1)2.11
Crystal size (mm)1.00 × 0.50 × 0.30
Data collection
DiffractometerSiemens P4
diffractometer
Absorption correctionNumerical
(Stoe & Cie, 1996)
Tmin, Tmax0.459, 0.623
No. of measured, independent and
observed [I > 2σ(I)] reflections
3964, 3189, 2659
Rint0.012
(sin θ/λ)max1)0.756
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.035, 0.066, 1.07
No. of reflections3189
No. of parameters207
No. of restraints1
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.93, 0.73
Absolute structureFlack (1983)
Absolute structure parameter0.01 (2)

Computer programs: XSCANS (Siemens, 1996), XSCANS, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 1998), SHELXL97.

Selected geometric parameters (Å, º) top
I1—C32.191 (4)C2—C71.518 (6)
S1—O21.428 (3)C2—C31.551 (5)
S1—O11.440 (3)C3—C41.521 (5)
S1—C111.771 (4)C4—C51.531 (5)
S1—C51.807 (3)C5—C61.522 (5)
C2—C81.525 (7)
O2—S1—O1119.43 (19)C11—S1—C5104.03 (17)
O2—S1—C11108.65 (17)C4—C3—C2115.5 (3)
O1—S1—C11107.54 (18)C4—C3—I1108.7 (2)
O2—S1—C5108.44 (18)C2—C3—I1111.9 (2)
O1—S1—C5107.69 (17)C3—C4—C5114.6 (3)
C1—C2—C3—C4175.4 (4)C3—C4—C5—S1179.4 (3)
C2—C3—C4—C5172.7 (3)C11—S1—C5—C4168.3 (2)
 

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