Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801007528/om6025sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801007528/om6025Isup2.hkl |
CCDC reference: 170761
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- Disorder in main residue
- R factor = 0.040
- wR factor = 0.121
- Data-to-parameter ratio = 14.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_301 Alert C Main Residue Disorder ........................ 11.00 Perc.
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
2-Chloro-2-propyl mesityl sulfone, (I), was prepared from mesityl 2-propyl sulfone by treatment with CCl4-powdered KOH-tert-BuOH (Hua, 1979). Column chromatography (silica gel, benzene/choroform) afforded colorless crystals (m.p. 360–362 K). Recrystallization from hexanes provided crystals with the same m.p., and were used in this study
The sum of the site occupancy values for C12 and C13 as well as Cl3 and Cl2 were restrained to 1.0. and the site-occupancy sum for each of the two disordered Cl/C sites was also restrained to 1.0. The C10—C and C10—Cl distances of the disordered C and Cl atoms were restrained to chemically reasonable distances of 1.54 and 1.76%A, respectively, and the C10—C12—Cl2 and C10—C13—Cl3 angles were restrained so that the C10—C12 and C10—Cl2 as well as the C10—C13 and C10—Cl3 bond vectors would be collinear. Without this restraint, the disordered Cl and C atoms refined to decidedly non-tetrahedral geometry with unacceptable displacement parameters. The restraint used to accomplish the bond vector collinearity was the SHELXL97 command: DANG 0.22 0.001 C12 Cl2 C13 Cl3. The 0.22 value is the difference between the restrained C10—C and C10—Cl distances given above. The Cl atoms were refined anisotropically. A satisfactory anisotropic refinement of the two disordered C atoms could not be attained so they were refined isotropically with a restraint to force both of their thermal displacements to be equal to that of C13. 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 are riding. Although tetrahedral geometry of the α-chloroisopropyl 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: SIR92 (Burla et al., 1989); program(s) used to refine structure: LS in TEXSAN and SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP (Johnson, 1965) in TEXSAN; software used to prepare material for publication: TEXSAN, SHELXL97, and PLATON (Spek, 2000).
C12H17ClO2S | F(000) = 276 |
Mr = 260.70 | Dx = 1.336 Mg m−3 |
Triclinic, P1 | Melting point = 360–362 K |
a = 9.237 (2) Å | Mo Kα radiation, λ = 0.71069 Å |
b = 9.4592 (13) Å | Cell parameters from 25 reflections |
c = 8.2079 (6) Å | θ = 12.5–12.9° |
α = 99.333 (9)° | µ = 0.44 mm−1 |
β = 93.671 (11)° | T = 296 K |
γ = 66.342 (14)° | Fragment, colorless |
V = 648.23 (18) Å3 | 0.41 × 0.36 × 0.20 mm |
Z = 2 |
Rigaku AFC-5S diffractometer | 1805 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.012 |
Graphite monochromator | θmax = 25.0°, θmin = 2.4° |
ω scans | h = 0→10 |
Absorption correction: ψ scan (North et al., 1968) | k = −10→11 |
Tmin = 0.853, Tmax = 0.916 | l = −9→9 |
2442 measured reflections | 3 standard reflections every 100 reflections |
2286 independent reflections | intensity decay: 0.5% |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.040 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0632P)2 + 0.2754P] where P = (Fo2 + 2Fc2)/3 |
2286 reflections | (Δ/σ)max < 0.001 |
160 parameters | Δρmax = 0.31 e Å−3 |
10 restraints | Δρmin = −0.26 e Å−3 |
C12H17ClO2S | γ = 66.342 (14)° |
Mr = 260.70 | V = 648.23 (18) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.237 (2) Å | Mo Kα radiation |
b = 9.4592 (13) Å | µ = 0.44 mm−1 |
c = 8.2079 (6) Å | T = 296 K |
α = 99.333 (9)° | 0.41 × 0.36 × 0.20 mm |
β = 93.671 (11)° |
Rigaku AFC-5S diffractometer | 1805 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.012 |
Tmin = 0.853, Tmax = 0.916 | 3 standard reflections every 100 reflections |
2442 measured reflections | intensity decay: 0.5% |
2286 independent reflections |
R[F2 > 2σ(F2)] = 0.040 | 10 restraints |
wR(F2) = 0.121 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.06 | Δρmax = 0.31 e Å−3 |
2286 reflections | Δρmin = −0.26 e Å−3 |
160 parameters |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Cl(2) | 0.4552 (3) | 0.0802 (2) | 0.3168 (2) | 0.0771 (4) | 0.800 (4) |
Cl(3) | 0.6037 (11) | 0.1583 (13) | 0.0750 (5) | 0.103 (4) | 0.198 (4) |
S1 | 0.31961 (7) | 0.39768 (7) | 0.23486 (7) | 0.0442 (2) | |
O1 | 0.2416 (2) | 0.4477 (2) | 0.3919 (2) | 0.0616 (5) | |
O2 | 0.3671 (2) | 0.5059 (2) | 0.1729 (3) | 0.0648 (5) | |
C1 | 0.2026 (2) | 0.3316 (3) | 0.0846 (3) | 0.0385 (5) | |
C2 | 0.0913 (3) | 0.2802 (3) | 0.1366 (3) | 0.0420 (5) | |
C3 | 0.0099 (3) | 0.2220 (3) | 0.0152 (3) | 0.0499 (6) | |
C4 | 0.0297 (3) | 0.2155 (3) | −0.1512 (3) | 0.0521 (6) | |
C5 | 0.1340 (3) | 0.2729 (3) | −0.1966 (3) | 0.0522 (6) | |
C6 | 0.2214 (3) | 0.3323 (3) | −0.0846 (3) | 0.0453 (6) | |
C7 | 0.3255 (4) | 0.3953 (4) | −0.1576 (4) | 0.0708 (8) | |
C8 | 0.0474 (4) | 0.2875 (4) | 0.3131 (3) | 0.0630 (8) | |
C9 | −0.0611 (4) | 0.1495 (4) | −0.2777 (4) | 0.0785 (10) | |
C10 | 0.5035 (3) | 0.2275 (3) | 0.2586 (3) | 0.0521 (6) | |
C11 | 0.6007 (3) | 0.2854 (4) | 0.3967 (4) | 0.0692 (9) | |
C12 | 0.463 (5) | 0.093 (3) | 0.302 (3) | 0.0544 (16)* | 0.199 (4) |
C13 | 0.6004 (9) | 0.1585 (8) | 0.1013 (4) | 0.0544 (16)* | 0.801 (4) |
H3 | −0.0619 | 0.1856 | 0.0476 | 0.060* | |
H5 | 0.1464 | 0.2717 | −0.3084 | 0.063* | |
H7a | 0.3178 | 0.3793 | −0.2759 | 0.106* | |
H7b | 0.4331 | 0.3416 | −0.1254 | 0.106* | |
H7c | 0.2915 | 0.5049 | −0.1180 | 0.106* | |
H8a | −0.0251 | 0.2381 | 0.3144 | 0.094* | |
H8b | −0.0015 | 0.3946 | 0.3634 | 0.094* | |
H8c | 0.1409 | 0.2345 | 0.3736 | 0.094* | |
H9a | −0.1189 | 0.2258 | −0.3477 | 0.118* | |
H9b | −0.1336 | 0.1233 | −0.2227 | 0.118* | |
H9c | 0.0112 | 0.0575 | −0.3434 | 0.118* | |
H11a | 0.7006 | 0.2016 | 0.4104 | 0.104* | |
H11b | 0.5429 | 0.3192 | 0.4988 | 0.104* | |
H11c | 0.6180 | 0.3709 | 0.3656 | 0.104* | |
H12a | 0.4069 | 0.0603 | 0.2123 | 0.082* | 0.199 (4) |
H12b | 0.3993 | 0.1296 | 0.4000 | 0.082* | 0.199 (4) |
H12c | 0.5595 | 0.0068 | 0.3213 | 0.082* | 0.199 (4) |
H13a | 0.5397 | 0.1239 | 0.0171 | 0.082* | 0.801 (4) |
H13b | 0.6952 | 0.0714 | 0.1220 | 0.082* | 0.801 (4) |
H13c | 0.6274 | 0.2364 | 0.0652 | 0.082* | 0.801 (4) |
U11 | U22 | U33 | U12 | U13 | U23 | |
Cl(2) | 0.0816 (8) | 0.0680 (7) | 0.0767 (8) | −0.0178 (6) | −0.0056 (6) | 0.0313 (6) |
Cl(3) | 0.063 (3) | 0.138 (6) | 0.062 (3) | 0.004 (3) | 0.014 (3) | −0.001 (3) |
S1 | 0.0394 (3) | 0.0435 (3) | 0.0452 (4) | −0.0159 (3) | −0.0008 (2) | −0.0040 (2) |
O1 | 0.0544 (10) | 0.0735 (12) | 0.0456 (10) | −0.0229 (9) | 0.0040 (8) | −0.0175 (9) |
O2 | 0.0606 (12) | 0.0513 (10) | 0.0883 (15) | −0.0305 (9) | −0.0013 (10) | 0.0047 (10) |
C1 | 0.0362 (11) | 0.0397 (11) | 0.0356 (11) | −0.0120 (9) | −0.0014 (9) | 0.0035 (9) |
C2 | 0.0398 (12) | 0.0463 (12) | 0.0390 (12) | −0.0170 (10) | 0.0007 (9) | 0.0040 (10) |
C3 | 0.0420 (13) | 0.0523 (14) | 0.0560 (15) | −0.0217 (11) | −0.0036 (11) | 0.0037 (12) |
C4 | 0.0516 (14) | 0.0425 (13) | 0.0484 (14) | −0.0093 (11) | −0.0148 (11) | −0.0005 (11) |
C5 | 0.0593 (16) | 0.0546 (14) | 0.0324 (12) | −0.0121 (12) | −0.0037 (11) | 0.0075 (10) |
C6 | 0.0444 (13) | 0.0484 (13) | 0.0386 (12) | −0.0119 (11) | 0.0004 (10) | 0.0110 (10) |
C7 | 0.074 (2) | 0.093 (2) | 0.0568 (17) | −0.0374 (18) | 0.0061 (14) | 0.0286 (16) |
C8 | 0.0650 (17) | 0.091 (2) | 0.0452 (15) | −0.0442 (16) | 0.0091 (12) | 0.0049 (14) |
C9 | 0.083 (2) | 0.0664 (19) | 0.072 (2) | −0.0254 (17) | −0.0313 (17) | −0.0074 (16) |
C10 | 0.0425 (13) | 0.0568 (15) | 0.0479 (14) | −0.0142 (11) | −0.0077 (11) | 0.0010 (11) |
C11 | 0.0453 (15) | 0.087 (2) | 0.0553 (16) | −0.0161 (14) | −0.0226 (12) | −0.0069 (14) |
Cl(2)—C10 | 1.763 (3) | C12—H12b | 0.9600 |
Cl(3)—C10 | 1.712 (5) | C12—H12c | 0.9600 |
C12—C10 | 1.556 (8) | C13—H13a | 0.9600 |
C13—C10 | 1.517 (5) | C13—H13b | 0.9600 |
C11—C10 | 1.566 (3) | C13—H13c | 0.9600 |
S1—C10 | 1.839 (3) | C3—H3 | 0.9300 |
S1—O1 | 1.4326 (19) | C5—H5 | 0.9300 |
S1—O2 | 1.434 (2) | C8—H8a | 0.9600 |
S1—C1 | 1.789 (2) | C8—H8b | 0.9600 |
C1—C6 | 1.412 (3) | C8—H8c | 0.9600 |
C1—C2 | 1.414 (3) | C7—H7a | 0.9600 |
C2—C3 | 1.386 (3) | C7—H7b | 0.9600 |
C2—C8 | 1.513 (3) | C7—H7c | 0.9600 |
C3—C4 | 1.378 (4) | C9—H9a | 0.9600 |
C4—C5 | 1.376 (4) | C9—H9b | 0.9600 |
C4—C9 | 1.507 (4) | C9—H9c | 0.9600 |
C5—C6 | 1.383 (4) | C11—H11a | 0.9600 |
C6—C7 | 1.513 (4) | C11—H11b | 0.9600 |
C12—H12a | 0.9600 | C11—H11c | 0.9600 |
O2···C7 | 2.805 (4) | C7···C13 | 3.503 (7) |
O1···C8 | 2.765 (4) | C8···C12 | 3.53 (4) |
C2···C12 | 3.47 (4) | O2···C7i | 3.341 (4) |
C6···C13 | 3.577 (8) | O2···C9ii | 3.371 (4) |
C13—C10—C11 | 110.0 (3) | C10—C13—H13c | 109.5 |
C11—C10—C12 | 113.0 (13) | H12a—C12—H12b | 109.5 |
C11—C10—Cl(3) | 111.8 (4) | H12a—C12—H12c | 109.5 |
C12—C10—Cl(3) | 106.5 (9) | H12b—C12—H12c | 109.5 |
C13—C10—Cl(2) | 107.3 (3) | H13a—C13—H13b | 109.5 |
C11—C10—Cl(2) | 111.3 (2) | H13a—C13—H13c | 109.5 |
C13—C10—S1 | 113.4 (3) | H13b—C13—H13c | 109.5 |
C11—C10—S1 | 106.16 (17) | C4—C3—H3 | 118.3 |
C12—C10—S1 | 109.6 (15) | C2—C3—H3 | 118.3 |
O1—S1—O2 | 117.09 (12) | C4—C5—H5 | 118.3 |
O1—S1—C1 | 109.91 (11) | C6—C5—H5 | 118.3 |
O2—S1—C1 | 110.26 (12) | C2—C8—H8a | 109.5 |
O1—S1—C10 | 106.66 (12) | C2—C8—H8b | 109.5 |
O2—S1—C10 | 105.45 (12) | H8a—C8—H8b | 109.5 |
C1—S1—C10 | 106.84 (11) | C2—C8—H8c | 109.5 |
C6—C1—C2 | 120.6 (2) | H8a—C8—H8c | 109.5 |
C6—C1—S1 | 119.73 (17) | H8b—C8—H8c | 109.5 |
C2—C1—S1 | 119.66 (17) | C6—C7—H7a | 109.5 |
C3—C2—C1 | 117.4 (2) | C6—C7—H7b | 109.5 |
C3—C2—C8 | 116.2 (2) | H7a—C7—H7b | 109.5 |
C1—C2—C8 | 126.4 (2) | C6—C7—H7c | 109.5 |
C4—C3—C2 | 123.4 (2) | H7a—C7—H7c | 109.5 |
C5—C4—C3 | 117.4 (2) | H7b—C7—H7c | 109.5 |
C5—C4—C9 | 121.6 (3) | C4—C9—H9a | 109.5 |
C3—C4—C9 | 121.0 (3) | C4—C9—H9b | 109.5 |
C4—C5—C6 | 123.5 (2) | H9a—C9—H9b | 109.5 |
C5—C6—C1 | 117.6 (2) | C4—C9—H9c | 109.5 |
C5—C6—C7 | 115.8 (2) | H9a—C9—H9c | 109.5 |
C1—C6—C7 | 126.6 (2) | H9b—C9—H9c | 109.5 |
Cl(3)—C10—S1 | 109.8 (3) | C10—C11—H11a | 109.5 |
Cl(2)—C10—S1 | 108.68 (15) | C10—C11—H11b | 109.5 |
C10—C12—H12a | 109.5 | H11a—C11—H11b | 109.5 |
C10—C12—H12b | 109.5 | C10—C11—H11c | 109.5 |
C10—C12—H12c | 109.5 | H11a—C11—H11c | 109.5 |
C10—C13—H13a | 109.5 | H11b—C11—H11c | 109.5 |
C10—C13—H13b | 109.5 | ||
O1—S1—C1—C6 | 156.36 (19) | S1—C1—C6—C5 | 176.86 (17) |
O2—S1—C1—C6 | 25.8 (2) | C2—C1—C6—C7 | 174.9 (2) |
C10—S1—C1—C6 | −88.3 (2) | S1—C1—C6—C7 | −4.7 (4) |
O1—S1—C1—C2 | −23.2 (2) | O1—S1—C10—C13 | 179.4 (3) |
O2—S1—C1—C2 | −153.74 (18) | O2—S1—C10—C13 | −55.5 (3) |
C10—S1—C1—C2 | 92.2 (2) | C1—S1—C10—C13 | 61.9 (3) |
C6—C1—C2—C3 | 3.9 (3) | O1—S1—C10—C11 | −59.7 (2) |
S1—C1—C2—C3 | −176.52 (17) | O2—S1—C10—C11 | 65.4 (2) |
C6—C1—C2—C8 | −173.7 (2) | C1—S1—C10—C11 | −177.23 (18) |
S1—C1—C2—C8 | 5.9 (3) | O1—S1—C10—C12 | 62.7 (10) |
C1—C2—C3—C4 | −1.4 (4) | O2—S1—C10—C12 | −172.2 (10) |
C8—C2—C3—C4 | 176.4 (2) | C1—S1—C10—C12 | −54.9 (10) |
C2—C3—C4—C5 | −1.3 (4) | O1—S1—C10—Cl(3) | 179.3 (5) |
C2—C3—C4—C9 | 179.4 (2) | O2—S1—C10—Cl(3) | −55.6 (5) |
C3—C4—C5—C6 | 1.7 (4) | C1—S1—C10—Cl(3) | 61.8 (5) |
C9—C4—C5—C6 | −179.0 (2) | O1—S1—C10—Cl(2) | 60.12 (16) |
C4—C5—C6—C1 | 0.7 (4) | O2—S1—C10—Cl(2) | −174.72 (14) |
C4—C5—C6—C7 | −177.9 (2) | C1—S1—C10—Cl(2) | −57.39 (16) |
C2—C1—C6—C5 | −3.6 (3) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C12H17ClO2S |
Mr | 260.70 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 296 |
a, b, c (Å) | 9.237 (2), 9.4592 (13), 8.2079 (6) |
α, β, γ (°) | 99.333 (9), 93.671 (11), 66.342 (14) |
V (Å3) | 648.23 (18) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.44 |
Crystal size (mm) | 0.41 × 0.36 × 0.20 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.853, 0.916 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 2442, 2286, 1805 |
Rint | 0.012 |
(sin θ/λ)max (Å−1) | 0.596 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.040, 0.121, 1.06 |
No. of reflections | 2286 |
No. of parameters | 160 |
No. of restraints | 10 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.31, −0.26 |
Computer programs: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation,1996), MSC/AFC Diffractometer Control Software, PROCESS in TEXSAN (Molecular Structure Corporation, 1997), SIR92 (Burla et al., 1989), LS in TEXSAN and SHELXL97 (Sheldrick, 1997), ORTEP (Johnson, 1965) in TEXSAN, TEXSAN, SHELXL97, and PLATON (Spek, 2000).
Cl(2)—C10 | 1.763 (3) | C13—C10 | 1.517 (5) |
Cl(3)—C10 | 1.712 (5) | C11—C10 | 1.566 (3) |
C12—C10 | 1.556 (8) | S1—C10 | 1.839 (3) |
O2···C7 | 2.805 (4) | C7···C13 | 3.503 (7) |
O1···C8 | 2.765 (4) | C8···C12 | 3.53 (4) |
C2···C12 | 3.47 (4) | O2···C7i | 3.341 (4) |
C6···C13 | 3.577 (8) | O2···C9ii | 3.371 (4) |
C13—C10—C11 | 110.0 (3) | C11—C10—Cl(2) | 111.3 (2) |
C11—C10—C12 | 113.0 (13) | C13—C10—S1 | 113.4 (3) |
C11—C10—Cl(3) | 111.8 (4) | C11—C10—S1 | 106.16 (17) |
C12—C10—Cl(3) | 106.5 (9) | C12—C10—S1 | 109.6 (15) |
C13—C10—Cl(2) | 107.3 (3) |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x, −y+1, −z. |
Our recent observations that the 2-bromo-2-propyl (α-bromoisopropyl) group in crystalline 2-bromo-2-propyl mesityl sulfone exhibits significant rotational disorder (Chan-Yu-King et al., 2001), while the same group in crystalline 2-bromo-2-propyl phenyl sulfone is completely ordered (Robinson, et al., 2001) prompted us to examine the X-ray structure of 2-chloro-2-propyl mesityl sulfone, (I).
The structure of (I) (Fig. 1) shows the two sites of the α-chloroisopropyl group that are somewhat rotationally disordered. Restrained site-occupancy refinement of these sites produced the following values: Cl2 = 0.800 (4), C12 = 0.199 (10), Cl3 = 0.198 (4), C13 = 0.801 (4). Thus, ca 80% of the rotamers have their Cl atom near O1 of the sulfonyl group and ca 20% have their Cl atom near O2; the third rotamer does not exist in this structure. This small rotational disorder may be associated with the small intra- and intermolecular non-bonding distances. For example, the intramolecular distances O2···O7 and O1···C8 are, respectively, 0.41 and 0.45 Å less than the sum of their van der Waals radii, while C2···C12, C6···C13, C7···C13 and C8···C12 exceed this sum by, respectively, only 0.07, 0.18, 0.10 and 0.13 Å. Intermolecular distances O2···O7 and O2···C9 are larger than the sum of their van der Waals radii by, respectively, only 0.12 and 0.15 Å. The contact distances for the above interactions are given in Table 2. Free rotation of the α-chloroisopropyl group of (I) in solution is apparent from its 1H NMR (CDCl3) spectrum, which exhibits one sharp singlet (6H) for the isopropyl methyl groups.