Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006651/om6021sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006651/om6021Isup2.hkl |
CCDC reference: 165665
Key indicators
- Single-crystal X-ray study
- T = 120 K
- Mean (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
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.
The coordinates of H atoms were refined, while their isotropic displacement parameters were assigned as Uiso = 1.5Ueq of the attached atom.
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.
C3H9S+·CH3O3S− | Dx = 1.459 Mg m−3 |
Mr = 172.26 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pnma | Cell parameters from 7642 reflections |
a = 12.6157 (4) Å | θ = 2.5–30.0° |
b = 8.2419 (4) Å | µ = 0.62 mm−1 |
c = 7.5397 (8) Å | T = 120 K |
V = 783.96 (9) Å3 | Plate, colorless |
Z = 4 | 0.12 × 0.10 × 0.02 mm |
F(000) = 368 |
KappaCCD diffractometer (with Oxford Cryosystems Cryostream cooler) | 1222 independent reflections |
Radiation source: fine-focus sealed tube | 838 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.047 |
ω scans with κ offsets | θmax = 30.1°, θmin = 3.1° |
Absorption correction: multi-scan HKL SCALEPACK (Otwinowski & Minor 1997) | h = −17→17 |
Tmin = 0.936, Tmax = 0.988 | k = −11→11 |
7642 measured reflections | l = −10→10 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.039 | Only 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 reflections | Δρmax = 0.40 e Å−3 |
69 parameters | Δρmin = −0.37 e Å−3 |
0 restraints | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0067 (18) |
C3H9S+·CH3O3S− | V = 783.96 (9) Å3 |
Mr = 172.26 | Z = 4 |
Orthorhombic, Pnma | Mo Kα radiation |
a = 12.6157 (4) Å | µ = 0.62 mm−1 |
b = 8.2419 (4) Å | T = 120 K |
c = 7.5397 (8) Å | 0.12 × 0.10 × 0.02 mm |
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 = 0.988 | Rint = 0.047 |
7642 measured reflections |
R[F2 > 2σ(F2)] = 0.039 | 0 restraints |
wR(F2) = 0.089 | Only H-atom coordinates refined |
S = 1.02 | Δρmax = 0.40 e Å−3 |
1222 reflections | Δρmin = −0.37 e Å−3 |
69 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.67208 (5) | 0.2500 | 0.27070 (8) | 0.0207 (2) | |
O1 | 0.57403 (15) | 0.2500 | 0.1667 (2) | 0.0272 (5) | |
O2 | 0.68432 (11) | 0.10235 (18) | 0.37463 (18) | 0.0321 (4) | |
C1 | 0.7765 (2) | 0.2500 | 0.1161 (4) | 0.0259 (6) | |
H1A | 0.844 (3) | 0.2500 | 0.188 (4) | 0.039* | |
H1B | 0.7715 (17) | 0.152 (3) | 0.050 (3) | 0.039* | |
S2 | 0.51948 (6) | 0.7500 | 0.30929 (8) | 0.0249 (2) | |
C2 | 0.6201 (2) | 0.7500 | 0.1426 (4) | 0.0285 (7) | |
H2A | 0.582 (3) | 0.7500 | 0.017 (4) | 0.043* | |
H2B | 0.6628 (17) | 0.658 (3) | 0.165 (3) | 0.043* | |
C3 | 0.43915 (17) | 0.5829 (3) | 0.2433 (3) | 0.0288 (5) | |
H3A | 0.4185 (17) | 0.607 (3) | 0.123 (3) | 0.043* | |
H3B | 0.3798 (19) | 0.582 (3) | 0.321 (3) | 0.043* | |
H3C | 0.480 (2) | 0.490 (3) | 0.257 (3) | 0.043* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0226 (3) | 0.0211 (3) | 0.0183 (3) | 0.000 | 0.0001 (3) | 0.000 |
O1 | 0.0232 (10) | 0.0323 (11) | 0.0260 (10) | 0.000 | −0.0020 (8) | 0.000 |
O2 | 0.0370 (9) | 0.0307 (8) | 0.0286 (7) | −0.0008 (7) | −0.0002 (6) | 0.0120 (6) |
C1 | 0.0271 (16) | 0.0258 (16) | 0.0246 (14) | 0.000 | 0.0044 (12) | 0.000 |
S2 | 0.0235 (4) | 0.0318 (4) | 0.0196 (3) | 0.000 | −0.0010 (3) | 0.000 |
C2 | 0.0212 (14) | 0.0309 (17) | 0.0335 (16) | 0.000 | 0.0071 (13) | 0.000 |
C3 | 0.0262 (11) | 0.0237 (10) | 0.0364 (12) | −0.0011 (9) | 0.0046 (9) | 0.0030 (10) |
S1—O1 | 1.4646 (19) | S2—C3 | 1.781 (2) |
S1—O2 | 1.4556 (14) | S2—C3ii | 1.781 (2) |
S1—O2i | 1.4556 (14) | C2—H2A | 1.06 (3) |
S1—C1 | 1.759 (3) | C2—H2B | 0.95 (2) |
C1—H1A | 1.01 (3) | C3—H3A | 0.97 (2) |
C1—H1B | 0.95 (2) | C3—H3B | 0.95 (2) |
S2—C2 | 1.786 (3) | C3—H3C | 0.92 (3) |
O2i—S1—O1 | 112.20 (7) | C3ii—S2—C2 | 102.00 (10) |
O2—S1—O1 | 112.20 (7) | S2—C2—H2A | 107.7 (17) |
O2i—S1—O2 | 113.45 (12) | S2—C2—H2B | 106.1 (13) |
O1—S1—C1 | 106.11 (13) | H2A—C2—H2B | 114.7 (16) |
O2i—S1—C1 | 106.11 (8) | S2—C3—H3A | 105.0 (15) |
O2—S1—C1 | 106.11 (8) | S2—C3—H3B | 106.4 (15) |
S1—C1—H1A | 105.8 (18) | H3A—C3—H3B | 111.8 (19) |
S1—C1—H1B | 107.2 (13) | S2—C3—H3C | 107.1 (15) |
H1A—C1—H1B | 109.6 (15) | H3A—C3—H3C | 115 (2) |
C3—S2—C3ii | 101.31 (15) | H3B—C3—H3C | 111 (2) |
C3—S2—C2 | 102.00 (10) |
Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O2iii | 0.95 (2) | 2.54 (2) | 3.463 (2) | 163.5 (18) |
C2—H2A···O1iv | 1.06 (3) | 2.41 (3) | 3.382 (4) | 152 (2) |
C3—H3A···O1iv | 0.97 (2) | 2.48 (2) | 3.388 (3) | 156.0 (19) |
C3—H3B···O2v | 0.95 (2) | 2.44 (2) | 3.279 (3) | 147.3 (19) |
C3—H3C···O1 | 0.92 (3) | 2.41 (3) | 3.280 (2) | 157.1 (19) |
Symmetry codes: (iii) −x+3/2, −y, z−1/2; (iv) −x+1, y+1/2, −z; (v) −x+1, y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C3H9S+·CH3O3S− |
Mr | 172.26 |
Crystal system, space group | Orthorhombic, Pnma |
Temperature (K) | 120 |
a, b, c (Å) | 12.6157 (4), 8.2419 (4), 7.5397 (8) |
V (Å3) | 783.96 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.62 |
Crystal size (mm) | 0.12 × 0.10 × 0.02 |
Data collection | |
Diffractometer | KappaCCD diffractometer (with Oxford Cryosystems Cryostream cooler) |
Absorption correction | Multi-scan HKL SCALEPACK (Otwinowski & Minor 1997) |
Tmin, Tmax | 0.936, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7642, 1222, 838 |
Rint | 0.047 |
(sin θ/λ)max (Å−1) | 0.706 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.039, 0.089, 1.02 |
No. of reflections | 1222 |
No. of parameters | 69 |
H-atom treatment | Only H-atom coordinates refined |
Δρmax, Δρmin (e Å−3) | 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.
S1—O1 | 1.4646 (19) | S2—C2 | 1.786 (3) |
S1—O2 | 1.4556 (14) | S2—C3 | 1.781 (2) |
S1—C1 | 1.759 (3) | ||
O2—S1—O1 | 112.20 (7) | O2—S1—C1 | 106.11 (8) |
O2i—S1—O2 | 113.45 (12) | C3—S2—C3ii | 101.31 (15) |
O1—S1—C1 | 106.11 (13) | C3—S2—C2 | 102.00 (10) |
Symmetry codes: (i) x, −y+1/2, z; (ii) x, −y+3/2, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1B···O2iii | 0.95 (2) | 2.54 (2) | 3.463 (2) | 163.5 (18) |
C2—H2A···O1iv | 1.06 (3) | 2.41 (3) | 3.382 (4) | 152 (2) |
C3—H3A···O1iv | 0.97 (2) | 2.48 (2) | 3.388 (3) | 156.0 (19) |
C3—H3B···O2v | 0.95 (2) | 2.44 (2) | 3.279 (3) | 147.3 (19) |
C3—H3C···O1 | 0.92 (3) | 2.41 (3) | 3.280 (2) | 157.1 (19) |
Symmetry codes: (iii) −x+3/2, −y, z−1/2; (iv) −x+1, y+1/2, −z; (v) −x+1, y+1/2, −z+1. |
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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)