Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006894/ci6022sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006894/ci6022Isup2.hkl |
CCDC reference: 165670
2-Amino-5-mercapto-1,3,4-thiadiazol (3.0 g, 22.52 mmol) in dry CH2Cl2 (200 ml) was added slowly (for 2 h) under an argon atmosphere to methanethiosulfonyl chloride (2.6 g, 22.52 mmol) in dry CH2Cl2 (40 ml) and pyridine solution (1.8 g, 22.52 mmol), keeping the temperature at 277 K. The reaction mixture was vigorously stirred for 24 h. The pyridinium chloride was filtered off and the solution concentrated. The precipitate was isolated and washed with dry ethanol. The solid residue was purified by crystallization from dry ethanol to give a white solid (800 mg, 4.56 mmol; 20%). However, the formation of an unexpected by-product could be observed. Single crystals suitable for X-ray diffraction were obtained by recrystallization (three times) of the solid residue from dry ethanol at 243 K.
All H atoms were located by difference Fourier synthesis and refined with fixed individual displacement parameters [U(H) = 1.5 Ueq(Cmethyl), U(H) = 1.2 Ueq(C) or U(H) = 1.2 Ueq(N)] using a riding model with C—Haromatic = 0.95, C—Hmethyl = 0.98 and N—H = 0.88 Å. When the structure is refined in the centrosymmetric space group Pnma, both ions must individually possess some mirror symmetry. The methylsulfonate fulfils Cs symmetry with C1, S1 and O1 lying on the mirror plane. In the case of the pyridinium ring, the mirror plane bisects the C2—-C3 and C5—C6 bonds, and atoms N1 and C4 are disordered over two positions across the mirror plane and occupy the same positions. Refinement in Pnma results in wR2 = 0.2492 and R1 = 0.095 for all data. The results of the refinement carried out in Pnma also reveal that two atoms (N1 and C5) showing strange anisotropic displacement parameters (Fig. 2), which is an indication that the structure is actually acentric and the correct space group is Pna21. Furthermore, the geometric parameters of N1 and C4 indicate that the pyridinium ring is not disordered.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 1991).
C5H6N+·CH3SO3− | Dx = 1.525 Mg m−3 |
Mr = 175.20 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, Pna21 | Cell parameters from 512 reflections |
a = 11.0853 (9) Å | θ = 2–20° |
b = 8.1425 (7) Å | µ = 0.38 mm−1 |
c = 8.4530 (8) Å | T = 173 K |
V = 762.99 (12) Å3 | Block, colourless |
Z = 4 | 0.62 × 0.58 × 0.56 mm |
F(000) = 368 |
Siemens CCD three-circle diffractometer | 1658 independent reflections |
Radiation source: fine-focus sealed tube | 1593 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.033 |
ω scans | θmax = 28.6°, θmin = 3.1° |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | h = 0→14 |
Tmin = 0.799, Tmax = 0.816 | k = 0→10 |
7984 measured reflections | l = −11→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)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.098 | w = 1/[σ2(Fo2) + (0.0508P)2 + 0.5001P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
1658 reflections | Δρmax = 0.54 e Å−3 |
100 parameters | Δρmin = −0.31 e Å−3 |
1 restraint | Absolute structure: Flack (1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.21 (13) |
C5H6N+·CH3SO3− | V = 762.99 (12) Å3 |
Mr = 175.20 | Z = 4 |
Orthorhombic, Pna21 | Mo Kα radiation |
a = 11.0853 (9) Å | µ = 0.38 mm−1 |
b = 8.1425 (7) Å | T = 173 K |
c = 8.4530 (8) Å | 0.62 × 0.58 × 0.56 mm |
Siemens CCD three-circle diffractometer | 1658 independent reflections |
Absorption correction: empirical (using intensity measurements) (SADABS; Sheldrick, 1996) | 1593 reflections with I > 2σ(I) |
Tmin = 0.799, Tmax = 0.816 | Rint = 0.033 |
7984 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.098 | Δρmax = 0.54 e Å−3 |
S = 1.10 | Δρmin = −0.31 e Å−3 |
1658 reflections | Absolute structure: Flack (1983) |
100 parameters | Absolute structure parameter: 0.21 (13) |
1 restraint |
Experimental. ; |
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 | 0.70804 (5) | 0.74081 (6) | 0.20959 (9) | 0.02166 (16) | |
C1 | 0.7775 (2) | 0.5471 (3) | 0.1911 (4) | 0.0328 (6) | |
H1A | 0.7468 | 0.4917 | 0.0963 | 0.049* | |
H1B | 0.7592 | 0.4805 | 0.2846 | 0.049* | |
H1C | 0.8650 | 0.5613 | 0.1820 | 0.049* | |
O1 | 0.57840 (16) | 0.7098 (2) | 0.2277 (3) | 0.0317 (4) | |
O2 | 0.73535 (19) | 0.8309 (3) | 0.0654 (2) | 0.0302 (5) | |
O3 | 0.75862 (18) | 0.8141 (3) | 0.3516 (3) | 0.0308 (5) | |
N1 | 0.5102 (2) | 0.7336 (3) | 0.5372 (3) | 0.0270 (6) | |
H1 | 0.5187 | 0.7325 | 0.4337 | 0.032* | |
C2 | 0.5763 (3) | 0.6304 (4) | 0.6244 (3) | 0.0290 (6) | |
H2 | 0.6307 | 0.5565 | 0.5747 | 0.035* | |
C3 | 0.5652 (3) | 0.6318 (4) | 0.7865 (3) | 0.0312 (7) | |
H3 | 0.6123 | 0.5597 | 0.8496 | 0.037* | |
C4 | 0.4852 (3) | 0.7389 (3) | 0.8564 (3) | 0.0285 (7) | |
H4 | 0.4768 | 0.7414 | 0.9683 | 0.034* | |
C5 | 0.4171 (3) | 0.8426 (4) | 0.7628 (3) | 0.0281 (6) | |
H5 | 0.3608 | 0.9160 | 0.8094 | 0.034* | |
C6 | 0.4317 (3) | 0.8384 (4) | 0.6020 (3) | 0.0280 (6) | |
H6 | 0.3861 | 0.9100 | 0.5365 | 0.034* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0253 (3) | 0.0225 (3) | 0.0172 (3) | −0.00016 (18) | −0.0001 (3) | −0.0007 (3) |
C1 | 0.0459 (15) | 0.0268 (12) | 0.0258 (13) | 0.0061 (10) | −0.0014 (12) | −0.0016 (12) |
O1 | 0.0294 (9) | 0.0437 (10) | 0.0221 (10) | −0.0030 (7) | 0.0009 (8) | 0.0004 (9) |
O2 | 0.0357 (12) | 0.0303 (12) | 0.0246 (10) | −0.0016 (8) | 0.0014 (8) | 0.0069 (8) |
O3 | 0.0369 (13) | 0.0326 (13) | 0.0231 (10) | −0.0027 (9) | −0.0031 (8) | −0.0073 (9) |
N1 | 0.0294 (14) | 0.0331 (13) | 0.0184 (10) | −0.0015 (10) | 0.0031 (9) | −0.0040 (9) |
C2 | 0.0255 (14) | 0.0273 (17) | 0.0342 (14) | 0.0030 (13) | 0.0037 (11) | −0.0026 (11) |
C3 | 0.0326 (16) | 0.0291 (17) | 0.0318 (14) | −0.0008 (13) | −0.0064 (12) | 0.0067 (11) |
C4 | 0.0326 (16) | 0.0358 (18) | 0.0172 (13) | −0.0048 (11) | −0.0009 (12) | −0.0006 (10) |
C5 | 0.0278 (14) | 0.0269 (14) | 0.0296 (13) | 0.0031 (11) | 0.0024 (10) | −0.0024 (10) |
C6 | 0.0233 (14) | 0.0339 (16) | 0.0269 (12) | 0.0005 (11) | −0.0040 (10) | 0.0022 (12) |
S1—O3 | 1.453 (2) | C2—C3 | 1.376 (3) |
S1—O2 | 1.454 (2) | C2—H2 | 0.9500 |
S1—O1 | 1.467 (2) | C3—C4 | 1.377 (5) |
S1—C1 | 1.762 (3) | C3—H3 | 0.9500 |
C1—H1A | 0.9800 | C4—C5 | 1.382 (4) |
C1—H1B | 0.9800 | C4—H4 | 0.9500 |
C1—H1C | 0.9800 | C5—C6 | 1.369 (4) |
N1—C6 | 1.336 (4) | C5—H5 | 0.9500 |
N1—C2 | 1.336 (4) | C6—H6 | 0.9500 |
N1—H1 | 0.8800 | ||
O3—S1—O2 | 113.86 (11) | N1—C2—C3 | 119.7 (4) |
O3—S1—O1 | 111.26 (13) | N1—C2—H2 | 120.2 |
O2—S1—O1 | 112.23 (12) | C3—C2—H2 | 120.2 |
O3—S1—C1 | 105.83 (14) | C2—C3—C4 | 119.4 (3) |
O2—S1—C1 | 106.63 (15) | C2—C3—H3 | 120.3 |
O1—S1—C1 | 106.43 (12) | C4—C3—H3 | 120.3 |
S1—C1—H1A | 109.5 | C3—C4—C5 | 119.5 (3) |
S1—C1—H1B | 109.5 | C3—C4—H4 | 120.2 |
H1A—C1—H1B | 109.5 | C5—C4—H4 | 120.2 |
S1—C1—H1C | 109.5 | C6—C5—C4 | 119.2 (3) |
H1A—C1—H1C | 109.5 | C6—C5—H5 | 120.4 |
H1B—C1—H1C | 109.5 | C4—C5—H5 | 120.4 |
C6—N1—C2 | 122.2 (3) | N1—C6—C5 | 120.0 (3) |
C6—N1—H1 | 118.9 | N1—C6—H6 | 120.0 |
C2—N1—H1 | 118.9 | C5—C6—H6 | 120.0 |
C6—N1—C2—C3 | −0.7 (5) | C3—C4—C5—C6 | −0.9 (5) |
N1—C2—C3—C4 | 0.6 (6) | C2—N1—C6—C5 | 0.1 (5) |
C2—C3—C4—C5 | 0.2 (5) | C4—C5—C6—N1 | 0.7 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.88 | 1.87 | 2.730 (3) | 165 |
C4—H4···O1i | 0.95 | 2.48 | 3.313 (4) | 147 |
C2—H2···O2ii | 0.95 | 2.36 | 3.249 (4) | 155 |
C3—H3···O3ii | 0.95 | 2.46 | 3.288 (4) | 146 |
Symmetry codes: (i) x, y, z+1; (ii) −x+3/2, y−1/2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C5H6N+·CH3SO3− |
Mr | 175.20 |
Crystal system, space group | Orthorhombic, Pna21 |
Temperature (K) | 173 |
a, b, c (Å) | 11.0853 (9), 8.1425 (7), 8.4530 (8) |
V (Å3) | 762.99 (12) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.62 × 0.58 × 0.56 |
Data collection | |
Diffractometer | Siemens CCD three-circle diffractometer |
Absorption correction | Empirical (using intensity measurements) (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.799, 0.816 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7984, 1658, 1593 |
Rint | 0.033 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.098, 1.10 |
No. of reflections | 1658 |
No. of parameters | 100 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.54, −0.31 |
Absolute structure | Flack (1983) |
Absolute structure parameter | 0.21 (13) |
Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).
S1—O3 | 1.453 (2) | N1—C2 | 1.336 (4) |
S1—O2 | 1.454 (2) | C2—C3 | 1.376 (3) |
S1—O1 | 1.467 (2) | C3—C4 | 1.377 (5) |
S1—C1 | 1.762 (3) | C4—C5 | 1.382 (4) |
N1—C6 | 1.336 (4) | C5—C6 | 1.369 (4) |
O3—S1—O2 | 113.86 (11) | C6—N1—C2 | 122.2 (3) |
O3—S1—O1 | 111.26 (13) | N1—C2—C3 | 119.7 (4) |
O2—S1—O1 | 112.23 (12) | C2—C3—C4 | 119.4 (3) |
O3—S1—C1 | 105.83 (14) | C3—C4—C5 | 119.5 (3) |
O2—S1—C1 | 106.63 (15) | C6—C5—C4 | 119.2 (3) |
O1—S1—C1 | 106.43 (12) | N1—C6—C5 | 120.0 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···O1 | 0.88 | 1.87 | 2.730 (3) | 164.5 |
C4—H4···O1i | 0.95 | 2.48 | 3.313 (4) | 146.5 |
C2—H2···O2ii | 0.95 | 2.36 | 3.249 (4) | 155.0 |
C3—H3···O3ii | 0.95 | 2.46 | 3.288 (4) | 145.8 |
Symmetry codes: (i) x, y, z+1; (ii) −x+3/2, y−1/2, z+1/2. |
Under chemical conditions, numerous procedures are available for the conversion of thiols to the corresponding disulfides. Usual potent oxidizing agents, e.g. O2 in the presence of basic aluminia (Liu & Tong, 1979), super oxide anion O2- (Kim & Yon, 1981) nitro compounds (Riordan et al., 1966) and halogens can oxidize thiols to disulfides. The possibility of synthesizing disulfides exclusively from thiols and sulfonyl chlorides has received more attention (Schiller & Otto, 1876; Otto, 1882). We have focused our interest on the reaction of thiols with corresponding sulfonyl chlorides and extended it to the preparation of thiosulfonates (R–S–SO2–R) and disulfides (R–S–S–R). In the present work, we describe the reaction between methanethiosulfonyl chloride and 2-amino-5-mercapto-1,3,4-thiadiazol, which did not yield the expected disulfides (R–S–S–R) or to the less stable thiosulfonates (R–S–SO2–R).
Compound (I) (Fig. 1) crystallizes in the acentric space group Pna21. However, more than 80% of the atoms show perfect centrosymmetry, as suggested by the program PLATON (Spek, 1990). As a result, one might assume that the space group is Pnma. Our refinement, on the other hand, reveals that the higher symmetry is not real and the correct space group is Pna21. Apart from the N—H···O hydrogen bond, there are three short C—H···O contacts.