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In the title compound, C3H9S+.CH3O3S-, a thermal decomposition product of di­methyl sulfoxide, both cation and anion lie on mirror planes. In the cation, the S atom lies 0.792 (2) Å out of the plane defined by the three C atoms, with S-C distances of 1.781 (2) and 1.786 (3) Å. In the anion, the S-O distances are 1.4556 (14) and 1.4646 (19) Å, and the S-C distance is 1.759 (3) Å.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006651/om6021sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006651/om6021Isup2.hkl
Contains datablock I

CCDC reference: 165665

Key indicators

  • Single-crystal X-ray study
  • T = 120 K
  • Mean [sigma](S-O) = 0.002 Å
  • R factor = 0.039
  • wR factor = 0.089
  • Data-to-parameter ratio = 17.7

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry








Comment top

We have been studying the structure and mechanism of formation of colored products derived from resorcinarene macrocycles upon heating in dimethyl sulfoxide (DMSO) (Lewis et al., 1997, 2000; Davis et al., 1999). We isolated the title compound, (I), a decomposition product formed by prolonged heating of a solution of macrocycle in DMSO, and determined its structure to ascertain its identity. While 38 salts of the trimethylsulfonium ion and 62 salts of the methylsulfonate anion are present in the Cambridge Structural Database (December 2000, 224400 entries; Allen & Kennard, 1993), the structure of the title compound has not been previously reported. Decomposition of DMSO or its complexes to form trimethylsulfonium methanesulfonate has been previously reported as a result of heating (Banci, 1967; Arsenin et al., 1988) and γ irradiation (Gutierrez et al., 1977).

Both cation and anion lie across crystallographic mirrors. In the cation, the S atom lies 0.792 (2) Å out of the plane defined by the three C atoms. Geometric parameters (Table 1) are normal. Most of the H atoms are involved in C—H···O hydrogen bonding (Table 2)

Experimental top

The tetramethylresorc[4]arene, 2,8,14,20-tetramethylpentacyclo[19.3.1.13,7.19,13.115,19]- octacosa-1(25),3,5,7(28),9,11,13 (27),15,17,19 (26),21,23-dodecaene- 4,6,10,12,16,18,22,24-octol (250 mg, 0.4596 mmol) was placed in a sealed tube along with 12 ml of DMSO and 3 ml of water. The mixture was heated at 493 K for 36 h. An aliquot was removed, and the solvent evaporated, yielding colorless crystals of the title compound.

Refinement top

The coordinates of H atoms were refined, while their isotropic displacement parameters were assigned as Uiso = 1.5Ueq of the attached atom.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO and SCALEPACK; data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. The atom-umbering scheme for (I) with ellipsoids at the 50% probability level.
trimethylsulfonium methanesulfonate top
Crystal data top
C3H9S+·CH3O3SDx = 1.459 Mg m3
Mr = 172.26Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, PnmaCell parameters from 7642 reflections
a = 12.6157 (4) Åθ = 2.5–30.0°
b = 8.2419 (4) ŵ = 0.62 mm1
c = 7.5397 (8) ÅT = 120 K
V = 783.96 (9) Å3Plate, colorless
Z = 40.12 × 0.10 × 0.02 mm
F(000) = 368
Data collection top
KappaCCD
diffractometer (with Oxford Cryosystems Cryostream cooler)
1222 independent reflections
Radiation source: fine-focus sealed tube838 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.047
ω scans with κ offsetsθmax = 30.1°, θmin = 3.1°
Absorption correction: multi-scan
HKL SCALEPACK (Otwinowski & Minor 1997)
h = 1717
Tmin = 0.936, Tmax = 0.988k = 1111
7642 measured reflectionsl = 1010
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)] = 0.039Only H-atom coordinates refined
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.0326P)2 + 0.2622P]
where P = (Fo2 + 2Fc2)/3
S = 1.02(Δ/σ)max < 0.001
1222 reflectionsΔρmax = 0.40 e Å3
69 parametersΔρmin = 0.37 e Å3
0 restraintsExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.0067 (18)
Crystal data top
C3H9S+·CH3O3SV = 783.96 (9) Å3
Mr = 172.26Z = 4
Orthorhombic, PnmaMo Kα radiation
a = 12.6157 (4) ŵ = 0.62 mm1
b = 8.2419 (4) ÅT = 120 K
c = 7.5397 (8) Å0.12 × 0.10 × 0.02 mm
Data collection top
KappaCCD
diffractometer (with Oxford Cryosystems Cryostream cooler)
1222 independent reflections
Absorption correction: multi-scan
HKL SCALEPACK (Otwinowski & Minor 1997)
838 reflections with I > 2σ(I)
Tmin = 0.936, Tmax = 0.988Rint = 0.047
7642 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0390 restraints
wR(F2) = 0.089Only H-atom coordinates refined
S = 1.02Δρmax = 0.40 e Å3
1222 reflectionsΔρmin = 0.37 e Å3
69 parameters
Special details top

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 (Å2) top
xyzUiso*/Ueq
S10.67208 (5)0.25000.27070 (8)0.0207 (2)
O10.57403 (15)0.25000.1667 (2)0.0272 (5)
O20.68432 (11)0.10235 (18)0.37463 (18)0.0321 (4)
C10.7765 (2)0.25000.1161 (4)0.0259 (6)
H1A0.844 (3)0.25000.188 (4)0.039*
H1B0.7715 (17)0.152 (3)0.050 (3)0.039*
S20.51948 (6)0.75000.30929 (8)0.0249 (2)
C20.6201 (2)0.75000.1426 (4)0.0285 (7)
H2A0.582 (3)0.75000.017 (4)0.043*
H2B0.6628 (17)0.658 (3)0.165 (3)0.043*
C30.43915 (17)0.5829 (3)0.2433 (3)0.0288 (5)
H3A0.4185 (17)0.607 (3)0.123 (3)0.043*
H3B0.3798 (19)0.582 (3)0.321 (3)0.043*
H3C0.480 (2)0.490 (3)0.257 (3)0.043*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0226 (3)0.0211 (3)0.0183 (3)0.0000.0001 (3)0.000
O10.0232 (10)0.0323 (11)0.0260 (10)0.0000.0020 (8)0.000
O20.0370 (9)0.0307 (8)0.0286 (7)0.0008 (7)0.0002 (6)0.0120 (6)
C10.0271 (16)0.0258 (16)0.0246 (14)0.0000.0044 (12)0.000
S20.0235 (4)0.0318 (4)0.0196 (3)0.0000.0010 (3)0.000
C20.0212 (14)0.0309 (17)0.0335 (16)0.0000.0071 (13)0.000
C30.0262 (11)0.0237 (10)0.0364 (12)0.0011 (9)0.0046 (9)0.0030 (10)
Geometric parameters (Å, º) top
S1—O11.4646 (19)S2—C31.781 (2)
S1—O21.4556 (14)S2—C3ii1.781 (2)
S1—O2i1.4556 (14)C2—H2A1.06 (3)
S1—C11.759 (3)C2—H2B0.95 (2)
C1—H1A1.01 (3)C3—H3A0.97 (2)
C1—H1B0.95 (2)C3—H3B0.95 (2)
S2—C21.786 (3)C3—H3C0.92 (3)
O2i—S1—O1112.20 (7)C3ii—S2—C2102.00 (10)
O2—S1—O1112.20 (7)S2—C2—H2A107.7 (17)
O2i—S1—O2113.45 (12)S2—C2—H2B106.1 (13)
O1—S1—C1106.11 (13)H2A—C2—H2B114.7 (16)
O2i—S1—C1106.11 (8)S2—C3—H3A105.0 (15)
O2—S1—C1106.11 (8)S2—C3—H3B106.4 (15)
S1—C1—H1A105.8 (18)H3A—C3—H3B111.8 (19)
S1—C1—H1B107.2 (13)S2—C3—H3C107.1 (15)
H1A—C1—H1B109.6 (15)H3A—C3—H3C115 (2)
C3—S2—C3ii101.31 (15)H3B—C3—H3C111 (2)
C3—S2—C2102.00 (10)
Symmetry codes: (i) x, y+1/2, z; (ii) x, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···O2iii0.95 (2)2.54 (2)3.463 (2)163.5 (18)
C2—H2A···O1iv1.06 (3)2.41 (3)3.382 (4)152 (2)
C3—H3A···O1iv0.97 (2)2.48 (2)3.388 (3)156.0 (19)
C3—H3B···O2v0.95 (2)2.44 (2)3.279 (3)147.3 (19)
C3—H3C···O10.92 (3)2.41 (3)3.280 (2)157.1 (19)
Symmetry codes: (iii) x+3/2, y, z1/2; (iv) x+1, y+1/2, z; (v) x+1, y+1/2, z+1.

Experimental details

Crystal data
Chemical formulaC3H9S+·CH3O3S
Mr172.26
Crystal system, space groupOrthorhombic, Pnma
Temperature (K)120
a, b, c (Å)12.6157 (4), 8.2419 (4), 7.5397 (8)
V3)783.96 (9)
Z4
Radiation typeMo Kα
µ (mm1)0.62
Crystal size (mm)0.12 × 0.10 × 0.02
Data collection
DiffractometerKappaCCD
diffractometer (with Oxford Cryosystems Cryostream cooler)
Absorption correctionMulti-scan
HKL SCALEPACK (Otwinowski & Minor 1997)
Tmin, Tmax0.936, 0.988
No. of measured, independent and
observed [I > 2σ(I)] reflections
7642, 1222, 838
Rint0.047
(sin θ/λ)max1)0.706
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.039, 0.089, 1.02
No. of reflections1222
No. of parameters69
H-atom treatmentOnly H-atom coordinates refined
Δρmax, Δρmin (e Å3)0.40, 0.37

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR (Altomare et al., 1994), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
S1—O11.4646 (19)S2—C21.786 (3)
S1—O21.4556 (14)S2—C31.781 (2)
S1—C11.759 (3)
O2—S1—O1112.20 (7)O2—S1—C1106.11 (8)
O2i—S1—O2113.45 (12)C3—S2—C3ii101.31 (15)
O1—S1—C1106.11 (13)C3—S2—C2102.00 (10)
Symmetry codes: (i) x, y+1/2, z; (ii) x, y+3/2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1B···O2iii0.95 (2)2.54 (2)3.463 (2)163.5 (18)
C2—H2A···O1iv1.06 (3)2.41 (3)3.382 (4)152 (2)
C3—H3A···O1iv0.97 (2)2.48 (2)3.388 (3)156.0 (19)
C3—H3B···O2v0.95 (2)2.44 (2)3.279 (3)147.3 (19)
C3—H3C···O10.92 (3)2.41 (3)3.280 (2)157.1 (19)
Symmetry codes: (iii) x+3/2, y, z1/2; (iv) x+1, y+1/2, z; (v) x+1, y+1/2, z+1.
 

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