Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801007516/om6024sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801007516/om6024Isup2.hkl |
CCDC reference: 170760
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.012 Å
- R factor = 0.034
- wR factor = 0.094
- Data-to-parameter ratio = 8.3
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 25.03 From the CIF: _reflns_number_total 1008 Count of symmetry unique reflns 1007 Completeness (_total/calc) 100.10% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 1 Fraction of Friedel pairs measured 0.001 Are heavy atom types Z>Si present yes WARNING: Large fraction of Friedel related reflns may be needed to determine absolute structure
2-Bromo-2-propyl phenyl sulfone, (I), was prepared from phenyl 2-propyl sulfone (Matthews, 1972) by treatment with CBr4–powdered KOH–tert-BuOH (Parady, 1977; see also, Meyers et al., 1977; Meyers, 1978), recrystallized from hexanes and used in this study (m.p. 367–368 K). Similar reactions with CBrCl3, CCl2Br2 or CBr2F2 instead of CBr4 produced varying yields of (I) (Parady, 1977).
The acentric polar space group of (I) was unexpected and caused difficulty with respect to the data/parameter ratio which resulted in higher than normal standard uncertainties. Also, since Friedel pairs were not collected, we were unable to use the results of the Flack parameter to determine whether or not the orientation of the crystal on the diffractometer and of the model were identical. However, a comparison of the wR(F2) values for the model and its inverse gave values of 0.094 and 0.097, respectively, indicating that the selected model is most likely correct. The rotational orientation of the methyl groups were refined by the circular Fourier method available in SHELXL97 (Sheldrick, 1997). All H atoms are riding.
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).
C9H11BrO2S | Dx = 1.657 Mg m−3 |
Mr = 263.15 | Melting point = 419–420 K |
Orthorhombic, Pna21 | Mo Kα radiation, λ = 0.71069 Å |
a = 21.134 (2) Å | Cell parameters from 25 reflections |
b = 6.2537 (11) Å | θ = 12.5–14.6° |
c = 7.979 (2) Å | µ = 4.06 mm−1 |
V = 1054.6 (4) Å3 | T = 296 K |
Z = 4 | Prism, colorless |
F(000) = 528 | 0.36 × 0.20 × 0.15 mm |
Rigaku AFC-5S diffractometer | 668 reflections with I > 2σ(I) |
Radiation source: sealed tube | Rint = 0.043 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = 0→25 |
Absorption correction: ψ scan (North et al., 1968) | k = −7→7 |
Tmin = 0.398, Tmax = 0.544 | l = 0→9 |
1917 measured reflections | 3 standard reflections every 100 reflections |
1008 independent reflections | intensity decay: 3.2% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0492P)2 + 0.1257P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.094 | (Δ/σ)max < 0.001 |
S = 1.01 | Δρmax = 0.31 e Å−3 |
1008 reflections | Δρmin = −0.27 e Å−3 |
121 parameters | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.0094 (15) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Flack (1983), 0 Friedel opposites, wR(F2) (inverse) 0.097 |
Secondary atom site location: difference Fourier map | Absolute structure parameter: 0.09 (2) |
C9H11BrO2S | V = 1054.6 (4) Å3 |
Mr = 263.15 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 21.134 (2) Å | µ = 4.06 mm−1 |
b = 6.2537 (11) Å | T = 296 K |
c = 7.979 (2) Å | 0.36 × 0.20 × 0.15 mm |
Rigaku AFC-5S diffractometer | 668 reflections with I > 2σ(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.043 |
Tmin = 0.398, Tmax = 0.544 | 3 standard reflections every 100 reflections |
1917 measured reflections | intensity decay: 3.2% |
1008 independent reflections |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.094 | Δρmax = 0.31 e Å−3 |
S = 1.01 | Δρmin = −0.27 e Å−3 |
1008 reflections | Absolute structure: Flack (1983), 0 Friedel opposites, wR(F2) (inverse) 0.097 |
121 parameters | Absolute structure parameter: 0.09 (2) |
1 restraint |
x | y | z | Uiso*/Ueq | ||
Br | 0.34405 (4) | 0.11425 (18) | 0.95490 (9) | 0.0798 (5) | |
S1 | 0.35712 (9) | 0.1208 (3) | 0.5784 (3) | 0.0510 (5) | |
O1 | 0.3573 (3) | −0.1059 (8) | 0.5880 (12) | 0.086 (2) | |
O2 | 0.3329 (3) | 0.2233 (11) | 0.4315 (8) | 0.0718 (17) | |
C1 | 0.4349 (3) | 0.2101 (12) | 0.6120 (9) | 0.0451 (18) | |
C2 | 0.4779 (4) | 0.0770 (15) | 0.6900 (13) | 0.065 (2) | |
C3 | 0.5415 (4) | 0.1520 (19) | 0.7061 (13) | 0.081 (3) | |
C4 | 0.5577 (4) | 0.3453 (18) | 0.6416 (12) | 0.073 (3) | |
C5 | 0.5150 (4) | 0.4728 (16) | 0.5649 (14) | 0.076 (3) | |
C6 | 0.4542 (4) | 0.4064 (12) | 0.5477 (11) | 0.057 (2) | |
C7 | 0.3092 (3) | 0.2238 (13) | 0.7476 (9) | 0.0473 (19) | |
C8 | 0.2421 (3) | 0.1324 (12) | 0.7296 (10) | 0.062 (3) | |
C9 | 0.3116 (4) | 0.4693 (11) | 0.7572 (12) | 0.0539 (19) | |
H2 | 0.4659 | −0.0564 | 0.7306 | 0.078* | |
H3 | 0.5717 | 0.0688 | 0.7605 | 0.097* | |
H4 | 0.5994 | 0.3913 | 0.6505 | 0.088* | |
H5 | 0.5272 | 0.6058 | 0.5239 | 0.091* | |
H6 | 0.4251 | 0.4929 | 0.4924 | 0.068* | |
H8a | 0.2158 | 0.1871 | 0.8178 | 0.092* | |
H8b | 0.2436 | −0.0207 | 0.7365 | 0.092* | |
H8c | 0.2248 | 0.1739 | 0.6231 | 0.092* | |
H9a | 0.2808 | 0.5188 | 0.8366 | 0.081* | |
H9b | 0.3025 | 0.5284 | 0.6489 | 0.081* | |
H9c | 0.3530 | 0.5137 | 0.7923 | 0.081* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br | 0.0675 (5) | 0.1134 (10) | 0.0587 (6) | −0.0113 (6) | −0.0062 (6) | 0.0336 (6) |
S1 | 0.0518 (11) | 0.0469 (13) | 0.0542 (13) | −0.0083 (10) | 0.0028 (9) | −0.0053 (10) |
O1 | 0.089 (4) | 0.047 (3) | 0.123 (6) | −0.012 (3) | 0.024 (4) | −0.021 (4) |
O2 | 0.063 (3) | 0.105 (4) | 0.047 (4) | 0.006 (3) | −0.013 (3) | 0.000 (4) |
C1 | 0.044 (4) | 0.048 (5) | 0.044 (4) | 0.006 (3) | −0.001 (4) | 0.003 (4) |
C2 | 0.060 (5) | 0.069 (7) | 0.066 (5) | 0.025 (5) | 0.011 (5) | 0.004 (4) |
C3 | 0.055 (5) | 0.133 (10) | 0.055 (5) | 0.038 (6) | 0.007 (4) | 0.013 (6) |
C4 | 0.045 (5) | 0.104 (8) | 0.070 (6) | −0.008 (5) | 0.009 (4) | −0.011 (6) |
C5 | 0.056 (5) | 0.074 (6) | 0.097 (7) | −0.006 (5) | 0.015 (6) | 0.014 (6) |
C6 | 0.050 (4) | 0.055 (5) | 0.065 (5) | 0.000 (4) | 0.001 (4) | 0.009 (4) |
C7 | 0.040 (4) | 0.058 (5) | 0.044 (4) | −0.007 (4) | −0.005 (3) | 0.007 (4) |
C8 | 0.040 (4) | 0.087 (6) | 0.058 (6) | −0.018 (4) | −0.003 (4) | 0.005 (4) |
C9 | 0.052 (5) | 0.047 (4) | 0.063 (5) | 0.006 (4) | 0.009 (4) | 0.001 (5) |
Br—C7 | 1.935 (7) | C7—C9 | 1.538 (11) |
S1—O1 | 1.420 (5) | C2—H2 | 0.9300 |
S1—O2 | 1.431 (7) | C3—H3 | 0.9300 |
S1—C1 | 1.757 (7) | C4—H4 | 0.9300 |
S1—C7 | 1.806 (8) | C5—H5 | 0.9300 |
C1—C2 | 1.381 (11) | C6—H6 | 0.9300 |
C1—C6 | 1.391 (10) | C8—H8a | 0.9600 |
C2—C3 | 1.429 (14) | C8—H8b | 0.9600 |
C3—C4 | 1.358 (12) | C8—H8c | 0.9600 |
C4—C5 | 1.351 (13) | C9—H9a | 0.9600 |
C5—C6 | 1.357 (11) | C9—H9b | 0.9600 |
C7—C8 | 1.537 (9) | C9—H9c | 0.9600 |
C6···C9 | 3.469 (12) | O2···C8ii | 3.414 (10) |
Br···C2 | 3.539 (9) | Br···C3iii | 3.555 (10) |
O1···C9i | 3.133 (10) | ||
O1—S1—O2 | 119.5 (5) | C1—C2—H2 | 121.3 |
O1—S1—C1 | 107.8 (4) | C3—C2—H2 | 121.3 |
O2—S1—C1 | 108.5 (3) | C4—C3—H3 | 120.2 |
O1—S1—C7 | 108.5 (4) | C2—C3—H3 | 120.2 |
O2—S1—C7 | 104.6 (3) | C5—C4—H4 | 119.0 |
C1—S1—C7 | 107.3 (3) | C3—C4—H4 | 119.0 |
C2—C1—C6 | 120.4 (7) | C6—C5—H5 | 120.1 |
C2—C1—S1 | 119.5 (6) | C5—C6—H6 | 119.7 |
C6—C1—S1 | 119.9 (6) | C1—C6—H6 | 119.7 |
C1—C2—C3 | 117.5 (9) | C7—C8—H8a | 109.5 |
C4—C3—C2 | 119.7 (9) | C7—C8—H8b | 109.5 |
C5—C4—C3 | 121.9 (9) | H8a—C8—H8b | 109.5 |
C4—C5—C6 | 119.8 (9) | C7—C8—H8c | 109.5 |
C4—C5—H5 | 120.1 | H8a—C8—H8c | 109.5 |
C5—C6—C1 | 120.7 (8) | H8b—C8—H8c | 109.5 |
C8—C7—C9 | 113.9 (7) | C7—C9—H9a | 109.5 |
C8—C7—S1 | 108.4 (5) | C7—C9—H9b | 109.5 |
C9—C7—S1 | 112.0 (5) | H9a—C9—H9b | 109.5 |
C8—C7—Br | 107.4 (5) | C7—C9—H9c | 109.5 |
C9—C7—Br | 107.4 (6) | H9a—C9—H9c | 109.5 |
S1—C7—Br | 107.5 (4) | H9b—C9—H9c | 109.5 |
O1—S1—C1—C2 | −19.8 (8) | C2—C1—C6—C5 | −1.9 (13) |
O2—S1—C1—C2 | −150.6 (7) | S1—C1—C6—C5 | −176.6 (7) |
C7—S1—C1—C2 | 96.9 (7) | O1—S1—C7—C8 | −59.1 (6) |
O1—S1—C1—C6 | 154.9 (7) | O2—S1—C7—C8 | 69.6 (6) |
O2—S1—C1—C6 | 24.1 (7) | C1—S1—C7—C8 | −175.3 (5) |
C7—S1—C1—C6 | −88.4 (7) | O1—S1—C7—C9 | 174.4 (6) |
C6—C1—C2—C3 | 1.9 (13) | O2—S1—C7—C9 | −57.0 (6) |
S1—C1—C2—C3 | 176.6 (7) | C1—S1—C7—C9 | 58.2 (6) |
C1—C2—C3—C4 | −1.7 (14) | O1—S1—C7—Br | 56.7 (5) |
C2—C3—C4—C5 | 1.4 (15) | O2—S1—C7—Br | −174.6 (4) |
C3—C4—C5—C6 | −1.3 (15) | C1—S1—C7—Br | −59.5 (4) |
C4—C5—C6—C1 | 1.6 (14) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, z−1/2; (iii) −x+1, −y, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C9H11BrO2S |
Mr | 263.15 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 296 |
a, b, c (Å) | 21.134 (2), 6.2537 (11), 7.979 (2) |
V (Å3) | 1054.6 (4) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 4.06 |
Crystal size (mm) | 0.36 × 0.20 × 0.15 |
Data collection | |
Diffractometer | Rigaku AFC-5S diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.398, 0.544 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 1917, 1008, 668 |
Rint | 0.043 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.094, 1.01 |
No. of reflections | 1008 |
No. of parameters | 121 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.31, −0.27 |
Absolute structure | Flack (1983), 0 Friedel opposites, wR(F2) (inverse) 0.097 |
Absolute structure parameter | 0.09 (2) |
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).
C6···C9 | 3.469 (12) | O2···C8ii | 3.414 (10) |
Br···C2 | 3.539 (9) | Br···C3iii | 3.555 (10) |
O1···C9i | 3.133 (10) |
Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y+1/2, z−1/2; (iii) −x+1, −y, z+1/2. |
The unexpected large rotational disorder of the 2-bromo-2-propyl group that characterized crystalline 2-bromo-2-propyl mesityl sulfone (Chan-Yu-King et al., 2001) prompted us to examine its less hindered analog, 2-bromo-2-propyl phenyl sulfone, (I).
The X-ray structure of (I), shown in Fig. 1 with its atom numbering, shows it to be a single rotamer, completely devoid of rotational disorder. The Br atom of this rotamer resides on the side of the sulfonyl group adjacent to O1. There is little steric interaction in (I), the most prominent being C6···C9 and Br···C2 which are, respectively, 0.07 Å greater than and 0.01 Å less than the sum of their van der Waals radii. The shortest intermolecular distances are O1···C9, O2···C8, and Br···C3 which are, respectively, -0.09 Å less than, 0.19 Å greater than, and 0.01 Å greater than the sum of their van der Waals radii. The shortest intra- and intermolecular contact distances are given in Table 1. The intermolecular packing is shown by Fig. 2.