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2–Propyl mesityl sulfone, C12H18O2S, (I), is entirely devoid of the rotational disorder displayed in the corresponding 2-bromo- and 2-chloro-2-propyl mesityl sulfones. Each mol­ecule of (I) hydrogen bonds with four other mol­ecules, each utilizing the acidic α-H atom of its 2-propyl group and a p-methyl-H atom as donors, and its two sulfonyl-O atoms as acceptors, resulting in a structure consisting of two-dimensional layers of hydrogen-bonded mol­ecules.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802017580/bt6197sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536802017580/bt6197Isup2.hkl
Contains datablock I

CCDC reference: 198981

Key indicators

  • Single-crystal X-ray study
  • T = 296 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.036
  • wR factor = 0.120
  • Data-to-parameter ratio = 15.4

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

We have reported that crystalline 2-bromo-2-propyl mesityl sulfone, (II) (Chan-Yu-King et al., 2001), 2-chloro-2-propyl mesityl sulfone, (III) (Meyers et al., 2001), and a related ketone, 2-bromo-2-propyl 2-(5-tert-butyl-1,3-xylyl) ketone, (IV) (Robinson, Sandrock et al., 2001), all exhibit rotational disorder, while 2-bromo-2-propyl phenyl sulfone, (V) (Robinson, Parady et al., 2001), and dichloromethyl phenyl sulfone, (VI) (Chan-Yu-King et al., 2002), do not. To learn more about the relationship between structure and rotational disorder, we have now examined crystalline 2-propyl mesityl sulfone, (I), the only 2-propyl mesityl structure in this series possessing an α-H atom.

The structure of (I), prepared as illustrated (see Scheme), is shown with its atom numbering in Fig. 1. An important aspect of this structure resides in its extensive hydrogen bonding, shown in Fig. 2. Each molecule hydrogen bonds with four mirror-image molecules, each utilizing the acidic α-H atom of its 2-propyl group and a p-methyl-H atom, as well as its two sulfonyl-O atoms as acceptors. Hydrogen-bond geometry is given in Table 1. As a consequence, the molecular packing consists of two-dimensional layers of intermoleculary hydrogen-bonded molecules. Four such layers, in an edge-on configuration normal to [100], are shown in Fig. 3.

This information suggests that rotational disorder in crystalline mesityl 2-propyl sulfones and ketones, e.g. (II), (III) and (IV), is associated with a combination of the steric effect of the mesityl group and absence of intermolecular hydrogen bonding involving an acidic α-H atom. In such a situation, crystallization would provide a packing structure of molecules without a common conformation of their 2-propyl group. This reasoning would account for the absence of rotational disorder in (I) (possessing a mesityl group and an acidic α-H atom providing extensive intermolecular hydrogen bonding with the sulfonyl group), (V) (possessing neither a mesityl group nor α-H atom) and (VI) (possessing an α-H atom but no mesityl group).

The effect of intermolecular hydrogen bonding in reducing intermolecular proximity and, thus, rotational disorder, in the packing structure is illustrated by the following example. In compound (II), which exhibits extensive rotational disorder (Chan-Yu-King et al., 2001), the intermolecular distance between atoms O1 and Br1 is 0.13 Å greater than the sum of their van der Waals radii. But, in compound (I), showing no rotational disorder, the intermolecular distance between the corresponding, but ostensibly hydrogen-bonded atoms O1 and H10 is 0.21 Å less than the sum of their van der Waals radii, and even its O1···C10 distance is only 0.17 Å greater than the sum of its van der Waals radii.

Experimental top

Compound (I) was prepared from mesitylenethiol and 2-bromopropane; m.p. 347.5–349.0 K (literature: m.p. 353 K; Shostakovskii & Bobrov, 1969), 1H NMR (CDCl3, p.p.m.): δ 1.33, (d, J = 7 Hz, 6 H), 2.27 (s, 3 H), 2.68 (s, 6 H), 3.28 (hep, J = 7 Hz, 1 H), 6.98 (s, 2 H).

Refinement top

The rotational orientations of the methyl groups were determined by the circular Fourier refinement method available in SHELXL97 (Sheldrick, 1997). All H atoms were treated as riding, with C—H distances in the range 0.93–0.98 Å. All methyl groups were allowed to rotate but not to tip.

Computing details top

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-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000); software used to prepare material for publication: TEXSAN, SHELXL97, and PLATON (Spek, 2000).

Figures top
[Figure 1] Fig. 1. The molecular structure and atom-numbering scheme for (I), with displacement ellipsoids at the 50% probablilty level.
[Figure 2] Fig. 2. The hydrogen bonding in (I). Each of the four surrounding molecules is inverted relative to the central molecule.
[Figure 3] Fig. 3. The molecular packing in (I), viewed down [001]. An edge view of four discrete two-dimensional molecular layers can be seen parallel to (100). H atoms not involved in hydrogen bonding have been omitted for clarity.
2-Propyl mesityl sulfone top
Crystal data top
C12H18O2SDx = 1.215 Mg m3
Mr = 226.32Melting point: 353 K
Orthorhombic, PbcaMo Kα radiation, λ = 0.71069 Å
a = 18.728 (2) ÅCell parameters from 25 reflections
b = 17.0310 (16) Åθ = 16.6–17.8°
c = 7.758 (3) ŵ = 0.24 mm1
V = 2474.5 (9) Å3T = 296 K
Z = 8Prism, colorless
F(000) = 9760.50 × 0.30 × 0.21 mm
Data collection top
Rigaku AFC-5S
diffractometer
Rint = 0.018
Radiation source: fine-focus sealed tubeθmax = 25.0°, θmin = 2.2°
Graphite monochromatorh = 022
ω scansk = 020
2878 measured reflectionsl = 92
2189 independent reflections3 standard reflections every 100 reflections
1386 reflections with I > 2σ(I) intensity decay: 2.3%
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.036H-atom parameters constrained
wR(F2) = 0.120 w = 1/[σ2(Fo2) + (0.0609P)2 + 0.5143P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max = 0.001
2189 reflectionsΔρmax = 0.22 e Å3
142 parametersΔρmin = 0.22 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0046 (8)
Crystal data top
C12H18O2SV = 2474.5 (9) Å3
Mr = 226.32Z = 8
Orthorhombic, PbcaMo Kα radiation
a = 18.728 (2) ŵ = 0.24 mm1
b = 17.0310 (16) ÅT = 296 K
c = 7.758 (3) Å0.50 × 0.30 × 0.21 mm
Data collection top
Rigaku AFC-5S
diffractometer
Rint = 0.018
2878 measured reflections3 standard reflections every 100 reflections
2189 independent reflections intensity decay: 2.3%
1386 reflections with I > 2σ(I)
Refinement top
R[F2 > 2σ(F2)] = 0.0360 restraints
wR(F2) = 0.120H-atom parameters constrained
S = 1.02Δρmax = 0.22 e Å3
2189 reflectionsΔρmin = 0.22 e Å3
142 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.60692 (3)0.11120 (4)0.65916 (9)0.0460 (2)
O10.59804 (10)0.16247 (12)0.8045 (3)0.0676 (6)
O20.57660 (9)0.03436 (10)0.6747 (3)0.0620 (5)
C10.70020 (12)0.10381 (13)0.6124 (3)0.0394 (5)
C20.74233 (12)0.17221 (14)0.6269 (3)0.0438 (6)
C30.81501 (13)0.16497 (16)0.5951 (3)0.0526 (7)
C40.84738 (13)0.09515 (16)0.5506 (3)0.0533 (7)
C50.80384 (14)0.03023 (16)0.5338 (3)0.0521 (7)
C60.73103 (12)0.03167 (14)0.5625 (3)0.0443 (6)
C70.69147 (16)0.04496 (14)0.5362 (4)0.0619 (8)
C80.71563 (14)0.25325 (14)0.6717 (4)0.0609 (7)
C90.92635 (15)0.0899 (2)0.5182 (5)0.0828 (10)
C100.56837 (13)0.15653 (15)0.4733 (4)0.0548 (7)
C110.48909 (16)0.1714 (2)0.5102 (5)0.0893 (12)
C120.57917 (17)0.10706 (18)0.3139 (4)0.0700 (8)
H30.84340.20960.60440.063*
H50.82460.01710.50120.063*
H7A0.72280.08250.48340.093*
H7B0.65100.03620.46280.093*
H7C0.67560.06470.64560.093*
H8A0.75290.29090.65200.091*
H8B0.70180.25460.79080.091*
H8C0.67520.26580.60080.091*
H9A0.94830.05900.60710.124*
H9B0.94660.14170.51860.124*
H9C0.93460.06570.40830.124*
H100.59180.20730.45530.066*
H11A0.46700.19420.41040.134*
H11B0.48460.20670.60610.134*
H11C0.46600.12260.53720.134*
H12A0.55310.05880.32550.105*
H12B0.62910.09580.30020.105*
H12C0.56220.13520.21480.105*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0408 (3)0.0475 (4)0.0497 (4)0.0042 (3)0.0068 (3)0.0040 (3)
O10.0612 (12)0.0794 (13)0.0623 (13)0.0002 (10)0.0184 (10)0.0153 (10)
O20.0528 (10)0.0555 (11)0.0777 (14)0.0114 (8)0.0107 (10)0.0194 (10)
C10.0381 (12)0.0465 (13)0.0337 (12)0.0039 (10)0.0027 (10)0.0025 (10)
C20.0454 (13)0.0477 (13)0.0385 (12)0.0054 (10)0.0005 (11)0.0010 (11)
C30.0458 (13)0.0614 (16)0.0507 (15)0.0152 (12)0.0029 (12)0.0037 (13)
C40.0414 (14)0.0737 (19)0.0448 (15)0.0000 (12)0.0015 (12)0.0065 (14)
C50.0535 (15)0.0580 (15)0.0448 (15)0.0119 (13)0.0022 (12)0.0045 (13)
C60.0497 (14)0.0472 (13)0.0359 (12)0.0007 (11)0.0005 (11)0.0024 (11)
C70.0743 (19)0.0414 (14)0.0700 (19)0.0018 (13)0.0057 (16)0.0019 (14)
C80.0627 (15)0.0491 (14)0.0709 (19)0.0076 (13)0.0072 (15)0.0073 (14)
C90.0448 (16)0.115 (3)0.089 (2)0.0001 (17)0.0039 (16)0.028 (2)
C100.0435 (14)0.0494 (14)0.0714 (19)0.0042 (12)0.0043 (13)0.0144 (14)
C110.0523 (17)0.096 (2)0.119 (3)0.0122 (17)0.0044 (19)0.026 (2)
C120.0685 (18)0.079 (2)0.0625 (19)0.0067 (16)0.0157 (16)0.0069 (16)
Geometric parameters (Å, º) top
S1—O21.4316 (17)C7—H7A0.9600
S1—O11.436 (2)C7—H7B0.9600
S1—C101.788 (3)C7—H7C0.9600
S1—C11.789 (2)C8—H8A0.9600
C1—C61.412 (3)C8—H8B0.9600
C1—C21.411 (3)C8—H8C0.9600
C2—C31.389 (3)C9—H9A0.9600
C2—C81.509 (3)C9—H9B0.9600
C3—C41.379 (4)C9—H9C0.9600
C4—C51.380 (4)C10—H100.9800
C4—C91.503 (4)C11—H11A0.9600
C5—C61.382 (3)C11—H11B0.9600
C6—C71.515 (3)C11—H11C0.9600
C10—C121.510 (4)C12—H12A0.9600
C10—C111.533 (4)C12—H12B0.9600
C3—H30.9300C12—H12C0.9600
C5—H50.9300
O2—S1—O1116.34 (12)C6—C7—H7C109.5
O2—S1—C10107.62 (12)H7A—C7—H7C109.5
O1—S1—C10108.91 (13)H7B—C7—H7C109.5
O2—S1—C1109.89 (11)C2—C8—H8A109.5
O1—S1—C1108.36 (11)C2—C8—H8B109.5
C10—S1—C1105.15 (11)H8A—C8—H8B109.5
C6—C1—C2120.8 (2)C2—C8—H8C109.5
C6—C1—S1121.09 (17)H8A—C8—H8C109.5
C2—C1—S1118.16 (17)H8B—C8—H8C109.5
C3—C2—C1117.4 (2)C4—C9—H9A109.5
C3—C2—C8116.5 (2)C4—C9—H9B109.5
C1—C2—C8126.0 (2)H9A—C9—H9B109.5
C4—C3—C2123.5 (2)C4—C9—H9C109.5
C3—C4—C5117.1 (2)H9A—C9—H9C109.5
C3—C4—C9121.7 (3)H9B—C9—H9C109.5
C5—C4—C9121.2 (3)C12—C10—H10108.4
C4—C5—C6123.6 (2)C11—C10—H10108.4
C5—C6—C1117.6 (2)S1—C10—H10108.4
C5—C6—C7116.5 (2)C10—C11—H11A109.5
C1—C6—C7125.9 (2)C10—C11—H11B109.5
C12—C10—C11112.0 (3)H11A—C11—H11B109.5
C12—C10—S1111.43 (19)C10—C11—H11C109.5
C11—C10—S1108.2 (2)H11A—C11—H11C109.5
C4—C3—H3118.2H11B—C11—H11C109.5
C2—C3—H3118.2C10—C12—H12A109.5
C4—C5—H5118.2C10—C12—H12B109.5
C6—C5—H5118.2H12A—C12—H12B109.5
C6—C7—H7A109.5C10—C12—H12C109.5
C6—C7—H7B109.5H12A—C12—H12C109.5
H7A—C7—H7B109.5H12B—C12—H12C109.5
O2—S1—C1—C612.6 (2)C3—C4—C5—C61.4 (4)
O1—S1—C1—C6140.7 (2)C9—C4—C5—C6179.7 (3)
C10—S1—C1—C6102.9 (2)C4—C5—C6—C10.2 (4)
O2—S1—C1—C2167.34 (18)C4—C5—C6—C7179.4 (2)
O1—S1—C1—C239.2 (2)C2—C1—C6—C51.9 (3)
C10—S1—C1—C277.1 (2)S1—C1—C6—C5178.07 (18)
C6—C1—C2—C31.8 (3)C2—C1—C6—C7177.7 (2)
S1—C1—C2—C3178.12 (19)S1—C1—C6—C72.4 (3)
C6—C1—C2—C8177.4 (2)O2—S1—C10—C1255.8 (2)
S1—C1—C2—C82.7 (3)O1—S1—C10—C12177.25 (18)
C1—C2—C3—C40.1 (4)C1—S1—C10—C1261.3 (2)
C8—C2—C3—C4179.2 (3)O2—S1—C10—C1167.7 (2)
C2—C3—C4—C51.5 (4)O1—S1—C10—C1159.2 (2)
C2—C3—C4—C9179.7 (3)C1—S1—C10—C11175.2 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9C···O2i0.962.503.403 (4)158
C10—H10···O1ii0.982.513.395 (4)150
Symmetry codes: (i) x+3/2, y, z1/2; (ii) x, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formulaC12H18O2S
Mr226.32
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)18.728 (2), 17.0310 (16), 7.758 (3)
V3)2474.5 (9)
Z8
Radiation typeMo Kα
µ (mm1)0.24
Crystal size (mm)0.50 × 0.30 × 0.21
Data collection
DiffractometerRigaku AFC-5S
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
2878, 2189, 1386
Rint0.018
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.036, 0.120, 1.02
No. of reflections2189
No. of parameters142
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.22, 0.22

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-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2000), TEXSAN, SHELXL97, and PLATON (Spek, 2000).

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9C···O2i0.962.503.403 (4)158
C10—H10···O1ii0.982.513.395 (4)150
Symmetry codes: (i) x+3/2, y, z1/2; (ii) x, y+1/2, z1/2.
 

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