Methyl 4-tolyl sulfone

The title compound, C₈H₁₀O₂S, was prepared from the reaction of H₂O₂ and methyl 4-tolyl sulfane. The tolyl C atoms are coplanar, the largest deviation being 0.0143 (13) Å for the methyl C atom.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.109
• Data-to-parameter ratio = 20.2

checkCIF/PLATON results

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Alert level C
PLAT031_ALERT_4_C Refined Extinction Parameter within Range ......       3.00 Sigma
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

Methyl 4-tolyl sulfone, (I), is an important intermediate in the synthesis of the herbicide Mesotrione (Yang et al., 2006) and was obtained from the reaction of hydrogen peroxide and methyl 4-tolyl sulfane. The molecular structure of (I) is illustrated in Fig. 1. Atoms C1, C2, C3, C4, C5, C6, C7 and S1 are coplanar, the largest deviation being 0.0143 (13) Å for C7. The dihedral angles between the C1—C7/S1 plane and the O1/O2/S1 and C8/01/02 planes are 52.57 (7) and 89.65 (5)^o, respectively. C—H···O interactions in the crystal structure of (I) lead to the formation of hydrogen-bonded chains (Table 1 and Fig. 2).

Related literature

For related literature, see: Bahrami (2006); Yang et al. (2006).

S2. Experimental

The title compound was prepared from hydrogen peroxide and methyl 4-tolyl sulfane, according to the procedure of Bahrami (2006).

S3. Refinement

H atoms were added at calculated positions and refined using a riding model. H atoms were given isotropic displacement parameters equal to 1.2(or 1.5 for methyl H atoms) times the equivalent isotropic displacement parameters of their parent atoms and C—H distances were restrained to 0.93 Å for those bonded to phenyl ring, 0.96 Å for those bonded to methyl.

Computing details

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

	Fig. 1. The structure of (I), shown with 30% probability displacement ellipsoids.
	Fig. 2. View showing the C—H···O hydrogen bonding. [Symmetry code: (i) -x + 1, -y + 2, -z (ii) -x + 1, +y + 1/2, -z + 1/2].

Methyl 4-tolyl sulfone

Crystal data

C8H10O2S	F(000) = 360
Mr = 170.23	Dx = 1.336 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 5.7272 (2) Å	θ = 9.9–13.9°
b = 7.9162 (2) Å	µ = 0.33 mm^−1
c = 18.7857 (5) Å	T = 298 K
β = 96.514 (1)°	Prismatic, colorless
V = 846.20 (4) Å^3	0.25 × 0.20 × 0.20 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1773 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.021
Graphite monochromator	θmax = 28.2°, θmin = 2.2°
ω/2θ scans	h = −7→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −10→10
Tmin = 0.922, Tmax = 0.937	l = −25→25
11134 measured reflections	3 standard reflections every 60 min
2041 independent reflections	intensity decay: 0.3%

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.035	H-atom parameters constrained
wR(F^2) = 0.109	w = 1/[σ^2(Fo^2) + (0.0572P)^2 + 0.1531P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
2041 reflections	Δρmax = 0.26 e Å^−3
101 parameters	Δρmin = −0.24 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.009 (3)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
O1	0.2439 (2)	0.81084 (15)	0.06740 (6)	0.0696 (4)
O2	0.6068 (2)	0.9756 (2)	0.09536 (7)	0.0791 (4)
S1	0.35964 (7)	0.95683 (5)	0.099533 (19)	0.05110 (17)
C1	0.3139 (3)	0.96216 (17)	0.19100 (8)	0.0435 (3)
C3	0.4491 (3)	1.0388 (2)	0.31124 (9)	0.0556 (4)
H3	0.5635	1.0873	0.3441	0.067*
C2	0.4838 (3)	1.0346 (2)	0.23968 (9)	0.0525 (4)
H4	0.6195	1.0799	0.2245	0.063*
C4	0.2490 (3)	0.97301 (18)	0.33535 (8)	0.0502 (4)
C5	0.0814 (3)	0.9003 (2)	0.28502 (9)	0.0560 (4)
H7	−0.0544	0.8548	0.3001	0.067*
C6	0.1123 (3)	0.8943 (2)	0.21331 (8)	0.0524 (4)
H8	−0.0011	0.8451	0.1804	0.063*
C8	0.2140 (4)	1.1359 (2)	0.06245 (9)	0.0653 (5)
H9A	0.0484	1.1248	0.0653	0.098*
H9B	0.2416	1.1467	0.0132	0.098*
H9C	0.2720	1.2344	0.0885	0.098*
C7	0.2132 (4)	0.9822 (3)	0.41361 (10)	0.0734 (5)
H10A	0.3471	1.0351	0.4399	0.110*
H10B	0.1949	0.8702	0.4317	0.110*
H10C	0.0748	1.0472	0.4190	0.110*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0963 (10)	0.0634 (7)	0.0455 (6)	0.0132 (6)	−0.0075 (6)	−0.0105 (5)
O2	0.0540 (7)	0.1354 (13)	0.0490 (7)	0.0164 (7)	0.0107 (5)	0.0012 (7)
S1	0.0517 (3)	0.0644 (3)	0.0364 (2)	0.01429 (15)	0.00173 (15)	−0.00173 (14)
C1	0.0433 (7)	0.0488 (7)	0.0374 (7)	0.0055 (5)	0.0004 (5)	−0.0011 (5)
C3	0.0642 (10)	0.0577 (9)	0.0428 (8)	−0.0133 (7)	−0.0026 (7)	−0.0056 (6)
C2	0.0491 (8)	0.0612 (9)	0.0466 (9)	−0.0106 (6)	0.0029 (6)	−0.0016 (6)
C4	0.0619 (9)	0.0470 (7)	0.0417 (8)	0.0026 (6)	0.0067 (7)	0.0011 (6)
C5	0.0465 (8)	0.0677 (9)	0.0544 (9)	−0.0056 (7)	0.0084 (6)	0.0030 (7)
C6	0.0424 (7)	0.0647 (9)	0.0482 (8)	−0.0039 (6)	−0.0031 (6)	−0.0050 (7)
C8	0.0828 (12)	0.0649 (10)	0.0474 (9)	0.0176 (9)	0.0042 (8)	0.0067 (7)
C7	0.0960 (15)	0.0810 (12)	0.0448 (10)	−0.0068 (11)	0.0151 (9)	−0.0005 (8)

Geometric parameters (Å, º)

O1—S1	1.4313 (13)	C4—C7	1.509 (2)
O2—S1	1.4344 (14)	C5—C6	1.379 (2)
S1—C8	1.7487 (17)	C5—H7	0.9300
S1—C1	1.7677 (15)	C6—H8	0.9300
C1—C6	1.381 (2)	C8—H9A	0.9600
C1—C2	1.382 (2)	C8—H9B	0.9600
C3—C4	1.381 (2)	C8—H9C	0.9600
C3—C2	1.381 (2)	C7—H10A	0.9600
C3—H3	0.9300	C7—H10B	0.9600
C2—H4	0.9300	C7—H10C	0.9600
C4—C5	1.393 (2)
O1—S1—O2	118.25 (9)	C6—C5—C4	121.47 (15)
O1—S1—C8	108.01 (9)	C6—C5—H7	119.3
O2—S1—C8	108.88 (10)	C4—C5—H7	119.3
O1—S1—C1	108.45 (7)	C5—C6—C1	119.16 (14)
O2—S1—C1	107.85 (7)	C5—C6—H8	120.4
C8—S1—C1	104.55 (7)	C1—C6—H8	120.4
C6—C1—C2	120.72 (14)	S1—C8—H9A	109.5
C6—C1—S1	120.45 (11)	S1—C8—H9B	109.5
C2—C1—S1	118.83 (12)	H9A—C8—H9B	109.5
C4—C3—C2	121.76 (14)	S1—C8—H9C	109.5
C4—C3—H3	119.1	H9A—C8—H9C	109.5
C2—C3—H3	119.1	H9B—C8—H9C	109.5
C3—C2—C1	119.06 (15)	C4—C7—H10A	109.5
C3—C2—H4	120.5	C4—C7—H10B	109.5
C1—C2—H4	120.5	H10A—C7—H10B	109.5
C3—C4—C5	117.83 (14)	C4—C7—H10C	109.5
C3—C4—C7	120.72 (16)	H10A—C7—H10C	109.5
C5—C4—C7	121.45 (16)	H10B—C7—H10C	109.5
O1—S1—C1—C6	−29.76 (14)	S1—C1—C2—C3	−179.88 (12)
O2—S1—C1—C6	−158.93 (13)	C2—C3—C4—C5	0.4 (2)
C8—S1—C1—C6	85.30 (14)	C2—C3—C4—C7	−178.81 (16)
O1—S1—C1—C2	149.93 (12)	C3—C4—C5—C6	−0.2 (2)
O2—S1—C1—C2	20.76 (15)	C7—C4—C5—C6	178.95 (16)
C8—S1—C1—C2	−95.02 (14)	C4—C5—C6—C1	−0.1 (2)
C4—C3—C2—C1	−0.2 (2)	C2—C1—C6—C5	0.3 (2)
C6—C1—C2—C3	−0.2 (2)	S1—C1—C6—C5	−179.98 (12)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C8—H9B···O2^i	0.96	2.50	3.363 (2)	150
C3—H3···O1^ii	0.93	2.59	3.4665 (19)	158

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x+1, y+1/2, −z+1/2.