Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006687/om6022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006687/om6022Isup2.hkl |
CCDC reference: 165666
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.009 Å
- Disorder in main residue
- R factor = 0.055
- wR factor = 0.169
- Data-to-parameter ratio = 14.0
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 16.00 Perc. General Notes
FORMU_01 There is a discrepancy between the atom counts in the _chemical_formula_sum and the formula from the _atom_site* data. Atom count from _chemical_formula_sum:C12 H17 Br1 O2 S1 Atom count from the _atom_site data: C12.002 H17.00600 Br0.983 O2 S1 CELLZ_01 From the CIF: _cell_formula_units_Z 2 From the CIF: _chemical_formula_sum C12 H17 Br1 O2 S1 TEST: Compare cell contents of formula and atom_site data atom Z*formula cif sites diff C 24.00 24.00 0.00 H 34.00 34.01 -0.01 Br 2.00 1.97 0.03 O 4.00 4.00 0.00 S 2.00 2.00 0.00 Difference between formula and atom_site contents detected. ALERT: check formula stoichiometry or atom site occupancies.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
2-Bromo-2-propyl mesityl sulfone, (I), was prepared by treating a tetrahydrofuran solution of mesityl 2-propyl sulfone (Hua, 1979) with nBuLi followed by the addition of Br2 in hexane, as reported by Chan-Yu-King (1986) and Meyers et al. (1998), affording crystals (from hexanes) (m.p. 361–362 K). The m.p. and X-ray analysis of these crystals were identical to those obtained with the crystals from an acetone solution which evaporated leaving an oil which slowly crystallized on standing.
During refinement the sum of the site-occupancy factors for the disordered Br and C sites were restrained to values of 1.0 and 2.0, respectively. Also the total site occupancy of each disordered Br/C site was restrained to 1.0. In addition, the C10—Br and C10—C distances were restrained to chemically reasonable values of 1.91 and 1.54 Å, and the C10—Br—C vectors were restrained so that they would remain relatively linear. The Br atoms were refined anisotropically, while the disordered C atoms were refined isotropically. The rotational orientation of the C7, C8, and C9 methyl groups were refined by the circular Fourier method available in SHELXL97 (Sheldrick, 1997). All H atoms were treated as riding. Although tetrahedral geometry of the α-bromoisopropyl group was not forced during the refinement, Table 1 shows that the group is relatively well behaved.
Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: PROCESS in TEXSAN (Molecular Structure Corporation, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: LS in TEXSAN and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP in TEXSAN (Johnson, 1965); software used to prepare material for publication: TEXSAN, SHELXL97, and PLATON (Spek, 2000).
C12H17BrO2S | F(000) = 312 |
Mr = 305.23 | Dx = 1.528 Mg m−3 |
Triclinic, P1 | Melting point = 361–362 K |
a = 9.2865 (16) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 9.6572 (18) Å | Cell parameters from 24 reflections |
c = 8.2077 (18) Å | θ = 14.1–14.9° |
α = 98.813 (18)° | µ = 3.24 mm−1 |
β = 92.841 (17)° | T = 296 K |
γ = 65.794 (12)° | Irregular fragment, colorless |
V = 663.4 (2) Å3 | 0.30 × 0.22 × 0.21 mm |
Z = 2 |
Rigaku AFC-5S diffractometer | 1269 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.024 |
Graphite monochromator | θmax = 25.0°, θmin = 2.3° |
ω/2θ scans | h = −11→11 |
Absorption correction: ψ scan (North et al. 1968) | k = −11→11 |
Tmin = 0.444, Tmax = 0.506 | l = 0→9 |
2526 measured reflections | 3 standard reflections every 100 reflections |
2346 independent reflections | intensity decay: 0.6% |
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)] = 0.055 | H-atom parameters constrained |
wR(F2) = 0.169 | w = 1/[σ2(Fo2) + (0.0644P)2 + 1.0978P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
2346 reflections | Δρmax = 0.66 e Å−3 |
167 parameters | Δρmin = −0.61 e Å−3 |
14 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.037 (5) |
C12H17BrO2S | γ = 65.794 (12)° |
Mr = 305.23 | V = 663.4 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.2865 (16) Å | Mo Kα radiation |
b = 9.6572 (18) Å | µ = 3.24 mm−1 |
c = 8.2077 (18) Å | T = 296 K |
α = 98.813 (18)° | 0.30 × 0.22 × 0.21 mm |
β = 92.841 (17)° |
Rigaku AFC-5S diffractometer | 1269 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al. 1968) | Rint = 0.024 |
Tmin = 0.444, Tmax = 0.506 | 3 standard reflections every 100 reflections |
2526 measured reflections | intensity decay: 0.6% |
2346 independent reflections |
R[F2 > 2σ(F2)] = 0.055 | 14 restraints |
wR(F2) = 0.169 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.66 e Å−3 |
2346 reflections | Δρmin = −0.61 e Å−3 |
167 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Br1 | 0.6179 (4) | 0.2887 (4) | 0.4156 (4) | 0.1018 (16) | 0.327 (3) |
Br2 | 0.4640 (3) | 0.0775 (2) | 0.3236 (3) | 0.0839 (8) | 0.551 (4) |
Br3 | 0.6237 (13) | 0.1585 (15) | 0.0515 (10) | 0.114 (6) | 0.105 (4) |
S1 | 0.31680 (16) | 0.40056 (16) | 0.23108 (18) | 0.0505 (5) | |
O1 | 0.2389 (5) | 0.4457 (5) | 0.3891 (5) | 0.0666 (12) | |
O2 | 0.3596 (5) | 0.5100 (5) | 0.1681 (6) | 0.0710 (12) | |
C1 | 0.2039 (6) | 0.3339 (6) | 0.0815 (6) | 0.0428 (12) | |
C2 | 0.0953 (6) | 0.2811 (6) | 0.1351 (6) | 0.0477 (13) | |
C3 | 0.0171 (7) | 0.2220 (6) | 0.0138 (8) | 0.0579 (16) | |
C4 | 0.0376 (7) | 0.2175 (6) | −0.1522 (7) | 0.0577 (16) | |
C5 | 0.1378 (7) | 0.2761 (7) | −0.1987 (7) | 0.0601 (16) | |
C6 | 0.2217 (6) | 0.3360 (6) | −0.0862 (7) | 0.0507 (14) | |
C7 | 0.3229 (8) | 0.4008 (9) | −0.1608 (8) | 0.076 (2) | |
C8 | 0.0502 (8) | 0.2852 (9) | 0.3114 (7) | 0.0734 (19) | |
C9 | −0.0490 (9) | 0.1501 (8) | −0.2793 (9) | 0.086 (2) | |
C10 | 0.4941 (5) | 0.2393 (4) | 0.2452 (4) | 0.0665 (17) | |
C11 | 0.5961 (17) | 0.2888 (16) | 0.3755 (11) | 0.060 (4)* | 0.655 (10) |
C12 | 0.473 (3) | 0.1026 (15) | 0.299 (2) | 0.048 (7)* | 0.437 (11) |
C13 | 0.6035 (10) | 0.1677 (9) | 0.0923 (8) | 0.045 (2)* | 0.910 (11) |
H3 | −0.0522 | 0.1838 | 0.0465 | 0.070* | |
H5 | 0.1504 | 0.2758 | −0.3104 | 0.072* | |
H7a | 0.3102 | 0.3917 | −0.2782 | 0.115* | |
H7b | 0.4317 | 0.3447 | −0.1358 | 0.115* | |
H7c | 0.2907 | 0.5070 | −0.1156 | 0.115* | |
H8a | 0.0034 | 0.3897 | 0.3644 | 0.110* | |
H8b | 0.1428 | 0.2288 | 0.3698 | 0.110* | |
H8c | −0.0243 | 0.2396 | 0.3115 | 0.110* | |
H9a | −0.0883 | 0.2147 | −0.3636 | 0.129* | |
H9b | −0.1358 | 0.1436 | −0.2269 | 0.129* | |
H9c | 0.0221 | 0.0494 | −0.3278 | 0.129* | |
H11a | 0.5381 | 0.3306 | 0.4778 | 0.090* | 0.655 (10) |
H11b | 0.6223 | 0.3652 | 0.3383 | 0.090* | 0.655 (10) |
H11c | 0.6912 | 0.2013 | 0.3914 | 0.090* | 0.655 (10) |
H12a | 0.4140 | 0.0664 | 0.2180 | 0.071* | 0.437 (11) |
H12b | 0.4180 | 0.1347 | 0.4033 | 0.071* | 0.437 (11) |
H12c | 0.5752 | 0.0214 | 0.3101 | 0.071* | 0.437 (11) |
H13a | 0.5474 | 0.1371 | 0.0027 | 0.067* | 0.910 (11) |
H13b | 0.6939 | 0.0796 | 0.1173 | 0.067* | 0.910 (11) |
H13c | 0.6374 | 0.2418 | 0.0617 | 0.067* | 0.910 (11) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0659 (18) | 0.124 (3) | 0.085 (2) | −0.0254 (15) | −0.0363 (16) | −0.0228 (16) |
Br2 | 0.0893 (13) | 0.0624 (10) | 0.0941 (13) | −0.0200 (9) | −0.0128 (9) | 0.0297 (9) |
Br3 | 0.075 (7) | 0.158 (10) | 0.071 (7) | −0.019 (6) | 0.018 (5) | −0.017 (6) |
S1 | 0.0408 (8) | 0.0494 (9) | 0.0530 (9) | −0.0145 (6) | −0.0024 (6) | −0.0042 (6) |
O1 | 0.058 (2) | 0.078 (3) | 0.050 (2) | −0.022 (2) | 0.005 (2) | −0.017 (2) |
O2 | 0.065 (3) | 0.057 (2) | 0.097 (3) | −0.033 (2) | −0.006 (2) | 0.009 (2) |
C1 | 0.037 (3) | 0.043 (3) | 0.043 (3) | −0.011 (2) | −0.004 (2) | 0.005 (2) |
C2 | 0.043 (3) | 0.056 (3) | 0.043 (3) | −0.019 (3) | −0.002 (2) | 0.007 (2) |
C3 | 0.048 (3) | 0.060 (4) | 0.071 (4) | −0.027 (3) | −0.006 (3) | 0.010 (3) |
C4 | 0.051 (3) | 0.048 (3) | 0.057 (4) | −0.008 (3) | −0.011 (3) | −0.004 (3) |
C5 | 0.061 (4) | 0.066 (4) | 0.038 (3) | −0.012 (3) | −0.004 (3) | 0.004 (3) |
C6 | 0.042 (3) | 0.055 (3) | 0.048 (3) | −0.010 (3) | 0.004 (2) | 0.013 (3) |
C7 | 0.076 (5) | 0.100 (5) | 0.064 (4) | −0.041 (4) | 0.001 (3) | 0.027 (4) |
C8 | 0.074 (4) | 0.106 (5) | 0.053 (4) | −0.049 (4) | 0.008 (3) | 0.008 (4) |
C9 | 0.088 (5) | 0.071 (5) | 0.080 (5) | −0.025 (4) | −0.030 (4) | −0.011 (4) |
C10 | 0.053 (4) | 0.072 (4) | 0.060 (4) | −0.014 (3) | −0.002 (3) | −0.001 (3) |
Br1—C10 | 1.895 (2) | C3—H3 | 0.9300 |
Br2—C10 | 1.903 (2) | C11—H11a | 0.9600 |
Br3—C10 | 1.904 (2) | C11—H11b | 0.9600 |
C11—C10 | 1.543 (2) | C11—H11c | 0.9600 |
C12—C10 | 1.541 (2) | C12—H12a | 0.9600 |
C13—C10 | 1.539 (2) | C12—H12b | 0.9600 |
S1—O1 | 1.434 (4) | C12—H12c | 0.9600 |
S1—O2 | 1.440 (4) | C13—H13a | 0.9600 |
S1—C10 | 1.756 (5) | C13—H13b | 0.9600 |
S1—C1 | 1.790 (5) | C13—H13c | 0.9600 |
C1—C6 | 1.399 (7) | C7—H7a | 0.9600 |
C1—C2 | 1.416 (7) | C7—H7b | 0.9600 |
C2—C3 | 1.391 (7) | C7—H7c | 0.9600 |
C3—C4 | 1.377 (8) | C8—H8a | 0.9600 |
C4—C5 | 1.365 (8) | C8—H8b | 0.9600 |
C5—C6 | 1.389 (8) | C8—H8c | 0.9600 |
C2—C8 | 1.516 (8) | C9—H9a | 0.9600 |
C4—C9 | 1.516 (8) | C9—H9b | 0.9600 |
C6—C7 | 1.518 (8) | C9—H9c | 0.9600 |
C5—H5 | 0.9300 | ||
Br1—C10—C12 | 102.9 (9) | C2—C3—H3 | 118.5 |
Br1—C10—C13 | 106.0 (5) | C10—C11—H11a | 109.5 |
Br1—C10—S1 | 109.4 (2) | C10—C11—H11b | 109.5 |
C13—C10—C12 | 104.0 (7) | C10—C11—H11c | 109.5 |
C12—C10—S1 | 114.3 (10) | C10—C12—H12a | 109.5 |
C13—C10—S1 | 118.7 (4) | C10—C12—H12b | 109.5 |
Br2—C10—C11 | 105.6 (4) | C10—C12—H12c | 109.5 |
Br2—C10—C13 | 107.2 (4) | C10—C13—H13a | 109.5 |
Br2—C10—S1 | 112.9 (2) | C10—C13—H13b | 109.5 |
C13—C10—C11 | 103.9 (7) | C10—C13—H13c | 109.5 |
C11—C10—S1 | 107.4 (6) | H11a—C11—H11b | 109.5 |
Br3—C10—C11 | 104.7 (8) | H11a—C11—H11c | 109.5 |
Br3—C10—C12 | 106.0 (8) | H11b—C11—H11c | 109.5 |
Br3—C10—S1 | 116.2 (4) | H12a—C12—H12b | 109.5 |
C12—C10—C11 | 107.5 (10) | H12a—C12—H12c | 109.5 |
O1—S1—O2 | 117.7 (3) | H12b—C12—H12c | 109.5 |
O1—S1—C10 | 107.7 (2) | H13a—C13—H13b | 109.5 |
O2—S1—C10 | 105.9 (2) | H13a—C13—H13c | 109.5 |
O1—S1—C1 | 110.0 (2) | H13b—C13—H13c | 109.5 |
O2—S1—C1 | 109.9 (3) | C6—C7—H7a | 109.5 |
C10—S1—C1 | 104.89 (19) | C6—C7—H7b | 109.5 |
C6—C1—C2 | 120.6 (5) | C6—C7—H7c | 109.5 |
C6—C1—S1 | 120.2 (4) | H7a—C7—H7b | 109.5 |
C2—C1—S1 | 119.3 (4) | H7a—C7—H7c | 109.5 |
C3—C2—C1 | 117.2 (5) | H7b—C7—H7c | 109.5 |
C3—C2—C8 | 115.5 (5) | C2—C8—H8a | 109.5 |
C1—C2—C8 | 127.3 (5) | C2—C8—H8b | 109.5 |
C4—C3—C2 | 123.1 (6) | C2—C8—H8c | 109.5 |
C5—C4—C3 | 118.0 (5) | H8a—C8—H8b | 109.5 |
C5—C4—C9 | 121.1 (6) | H8a—C8—H8c | 109.5 |
C3—C4—C9 | 120.9 (7) | H8b—C8—H8c | 109.5 |
C4—C5—C6 | 122.8 (5) | C4—C9—H9a | 109.5 |
C5—C6—C1 | 118.2 (5) | C4—C9—H9b | 109.5 |
C5—C6—C7 | 115.2 (5) | C4—C9—H9c | 109.5 |
C1—C6—C7 | 126.5 (5) | H9a—C9—H9b | 109.5 |
C4—C5—H5 | 118.6 | H9a—C9—H9c | 109.5 |
C6—C5—H5 | 118.6 | H9b—C9—H9c | 109.5 |
C4—C3—H3 | 118.5 | ||
O1—S1—C1—C6 | 157.0 (4) | C2—C1—C6—C7 | 174.8 (5) |
O2—S1—C1—C6 | 25.9 (5) | S1—C1—C6—C7 | −4.4 (8) |
C10—S1—C1—C6 | −87.5 (4) | O1—S1—C10—C13 | −179.1 (5) |
O1—S1—C1—C2 | −22.3 (5) | O2—S1—C10—C13 | −52.4 (5) |
O2—S1—C1—C2 | −153.3 (4) | C1—S1—C10—C13 | 63.7 (5) |
C10—S1—C1—C2 | 93.3 (4) | O1—S1—C10—C12 | 57.4 (8) |
C6—C1—C2—C3 | 4.4 (8) | O2—S1—C10—C12 | −175.9 (8) |
S1—C1—C2—C3 | −176.3 (4) | C1—S1—C10—C12 | −59.7 (8) |
C6—C1—C2—C8 | −173.7 (6) | O1—S1—C10—C11 | −61.8 (5) |
S1—C1—C2—C8 | 5.5 (8) | O2—S1—C10—C11 | 64.9 (5) |
C1—C2—C3—C4 | −1.9 (8) | C1—S1—C10—C11 | −178.9 (5) |
C8—C2—C3—C4 | 176.4 (5) | O1—S1—C10—Br1 | −57.4 (3) |
C2—C3—C4—C5 | −1.0 (9) | O2—S1—C10—Br1 | 69.3 (3) |
C2—C3—C4—C9 | 179.2 (5) | C1—S1—C10—Br1 | −174.5 (3) |
C3—C4—C5—C6 | 1.6 (9) | O1—S1—C10—Br2 | 54.2 (3) |
C9—C4—C5—C6 | −178.7 (5) | O2—S1—C10—Br2 | −179.1 (2) |
C4—C5—C6—C1 | 0.9 (8) | C1—S1—C10—Br2 | −62.9 (3) |
C4—C5—C6—C7 | −178.0 (5) | O1—S1—C10—Br3 | −178.6 (6) |
C2—C1—C6—C5 | −4.0 (8) | O2—S1—C10—Br3 | −51.9 (6) |
S1—C1—C6—C5 | 176.8 (4) | C1—S1—C10—Br3 | 64.2 (6) |
Experimental details
Crystal data | |
Chemical formula | C12H17BrO2S |
Mr | 305.23 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 9.2865 (16), 9.6572 (18), 8.2077 (18) |
α, β, γ (°) | 98.813 (18), 92.841 (17), 65.794 (12) |
V (Å3) | 663.4 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 3.24 |
Crystal size (mm) | 0.30 × 0.22 × 0.21 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | ψ scan (North et al. 1968) |
Tmin, Tmax | 0.444, 0.506 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2526, 2346, 1269 |
Rint | 0.024 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.169, 1.03 |
No. of reflections | 2346 |
No. of parameters | 167 |
No. of restraints | 14 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.66, −0.61 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1996), MSC/AFC Diffractometer Control Software, PROCESS in TEXSAN (Molecular Structure Corporation, 1997), SHELXS97 (Sheldrick, 1990), LS in TEXSAN and SHELXL97 (Sheldrick, 1997), ORTEP in TEXSAN (Johnson, 1965), TEXSAN, SHELXL97, and PLATON (Spek, 2000).
Br1—C10 | 1.895 (2) | C12—C10 | 1.541 (2) |
Br2—C10 | 1.903 (2) | C13—C10 | 1.539 (2) |
Br3—C10 | 1.904 (2) | S1—C10 | 1.756 (5) |
C11—C10 | 1.543 (2) | ||
Br1—C10—C12 | 102.9 (9) | Br2—C10—S1 | 112.9 (2) |
Br1—C10—C13 | 106.0 (5) | C13—C10—C11 | 103.9 (7) |
Br1—C10—S1 | 109.4 (2) | C11—C10—S1 | 107.4 (6) |
C13—C10—C12 | 104.0 (7) | Br3—C10—C11 | 104.7 (8) |
C12—C10—S1 | 114.3 (10) | Br3—C10—C12 | 106.0 (8) |
C13—C10—S1 | 118.7 (4) | Br3—C10—S1 | 116.2 (4) |
Br2—C10—C11 | 105.6 (4) | C12—C10—C11 | 107.5 (10) |
Br2—C10—C13 | 107.2 (4) |
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Unlike related isopropyl sulfones, 2-propyl mesityl sulfone could not be α-brominated with CBrCl3 in powdered KOH–tert-BuOH, but was successfully brominated by treatment with nBuLi followed by Br2 (Chan-Yu-King, 1986), to provide 2-bromo-2-propyl mesityl sulfone, (I). In a study undertaken to determine why the initial synthetic attempt was unsuccessful (Meyers et al., 1998), (I) was prepared again and its stereochemistry examined by X-ray analysis. The X-ray structure of (I) is shown with atom numbering in Fig. 1.
A salient feature of the X-ray structure resides with the significant rotational disorder of the α-bromoisopropyl group, also shown in Fig. 1. Restrained site-occupancy refinement of the six disordered sites produced the following site-occupancy values: Br1 = 0.327 (3), C11 = 0.655 (10), Br2 = 0.551 (4), C12 = 0.437 (11), Br3 = 0.105 (4), and C13 = 0.910 (11). This disorder may be associated with the small intra- and intermolecular non-bonding distances. For example, the intramolecular distances O1···C8 and O2···C7 are 0.45 and 0.42 Å, respectively, less than the sum of their van der Waals radii, while C2···C12, C6···C13, C7···C13 and C8···C12 are larger by only 0.12, 0.18, 0.10 and 0.18 Å, respectively, and the intermolecular distances O2···C7 and O2···C9 are larger by only 0.18 and 0.17 Å, respectively. However, the NMR (CDCl3) spectrum of (I) exhibits one sharp singlet (6H) for the isopropyl methyl groups.