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The title compound, C5H6N+·CH3SO3-, shows pseudosymmetry. More than 80% of the structure is centrosymmetric, whereas the remaining atoms do not fulfil this symmetry, and the structure is actually non-centrosymmetric.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801006894/ci6022sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801006894/ci6022Isup2.hkl
Contains datablock I

CCDC reference: 165670

Key indicators

  • Single-crystal X-ray study
  • T = 173 K
  • Mean [sigma](C-C) = 0.004 Å
  • R factor = 0.037
  • wR factor = 0.098
  • Data-to-parameter ratio = 16.6

checkCIF results

No syntax errors found


Amber Alert Alert Level B:
PLAT_111 Alert B ADDSYM detects (pseudo) centre of symmetry ... 81 Perc Fit
Author response: see publ_section_comment and _publ_section_exptl_refinement
PLAT_112  Alert B ADDSYM Detects Additional (Pseudo) Symm. Elem.          m
Author response: see publ_section_comment and _publ_section_exptl_refinement
PLAT_113  Alert B ADDSYM suggests Pseudo/New Spacegroup ........       Pnma
Author response: see publ_section_comment and _publ_section_exptl_refinement
General Notes

REFLT_03 From the CIF: _diffrn_reflns_theta_max 28.55 From the CIF: _reflns_number_total 1658 Count of symmetry unique reflns 1035 Completeness (_total/calc) 160.19% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 623 Fraction of Friedel pairs measured 0.602 Are heavy atom types Z>Si present yes Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF.
0 Alert Level A = Potentially serious problem
3 Alert Level B = Potential problem
0 Alert Level C = Please check

Comment top

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–SO2R) 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–SO2R).

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.

Experimental top

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.

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. A perspective view of (I) with the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level
[Figure 2] Fig. 2. A perspective view of (I) refined in the centrosymmetric space group Pnma, with the atom-numbering scheme. Displacement ellipsoids are at the 50% probability level [symmetry codes: (A) x, -1/2 - y, z; (B) x, 1/2 - y, z].
(I) top
Crystal data top
C5H6N+·CH3SO3Dx = 1.525 Mg m3
Mr = 175.20Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pna21Cell parameters from 512 reflections
a = 11.0853 (9) Åθ = 2–20°
b = 8.1425 (7) ŵ = 0.38 mm1
c = 8.4530 (8) ÅT = 173 K
V = 762.99 (12) Å3Block, colourless
Z = 40.62 × 0.58 × 0.56 mm
F(000) = 368
Data collection top
Siemens CCD three-circle
diffractometer
1658 independent reflections
Radiation source: fine-focus sealed tube1593 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.033
ω scansθmax = 28.6°, θmin = 3.1°
Absorption correction: empirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
h = 014
Tmin = 0.799, Tmax = 0.816k = 010
7984 measured reflectionsl = 1110
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)] = 0.037H-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 reflectionsΔρmax = 0.54 e Å3
100 parametersΔρmin = 0.31 e Å3
1 restraintAbsolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.21 (13)
Crystal data top
C5H6N+·CH3SO3V = 762.99 (12) Å3
Mr = 175.20Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 11.0853 (9) ŵ = 0.38 mm1
b = 8.1425 (7) ÅT = 173 K
c = 8.4530 (8) Å0.62 × 0.58 × 0.56 mm
Data collection top
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 = 0.816Rint = 0.033
7984 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.098Δρmax = 0.54 e Å3
S = 1.10Δρmin = 0.31 e Å3
1658 reflectionsAbsolute structure: Flack (1983)
100 parametersAbsolute structure parameter: 0.21 (13)
1 restraint
Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.70804 (5)0.74081 (6)0.20959 (9)0.02166 (16)
C10.7775 (2)0.5471 (3)0.1911 (4)0.0328 (6)
H1A0.74680.49170.09630.049*
H1B0.75920.48050.28460.049*
H1C0.86500.56130.18200.049*
O10.57840 (16)0.7098 (2)0.2277 (3)0.0317 (4)
O20.73535 (19)0.8309 (3)0.0654 (2)0.0302 (5)
O30.75862 (18)0.8141 (3)0.3516 (3)0.0308 (5)
N10.5102 (2)0.7336 (3)0.5372 (3)0.0270 (6)
H10.51870.73250.43370.032*
C20.5763 (3)0.6304 (4)0.6244 (3)0.0290 (6)
H20.63070.55650.57470.035*
C30.5652 (3)0.6318 (4)0.7865 (3)0.0312 (7)
H30.61230.55970.84960.037*
C40.4852 (3)0.7389 (3)0.8564 (3)0.0285 (7)
H40.47680.74140.96830.034*
C50.4171 (3)0.8426 (4)0.7628 (3)0.0281 (6)
H50.36080.91600.80940.034*
C60.4317 (3)0.8384 (4)0.6020 (3)0.0280 (6)
H60.38610.91000.53650.034*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0253 (3)0.0225 (3)0.0172 (3)0.00016 (18)0.0001 (3)0.0007 (3)
C10.0459 (15)0.0268 (12)0.0258 (13)0.0061 (10)0.0014 (12)0.0016 (12)
O10.0294 (9)0.0437 (10)0.0221 (10)0.0030 (7)0.0009 (8)0.0004 (9)
O20.0357 (12)0.0303 (12)0.0246 (10)0.0016 (8)0.0014 (8)0.0069 (8)
O30.0369 (13)0.0326 (13)0.0231 (10)0.0027 (9)0.0031 (8)0.0073 (9)
N10.0294 (14)0.0331 (13)0.0184 (10)0.0015 (10)0.0031 (9)0.0040 (9)
C20.0255 (14)0.0273 (17)0.0342 (14)0.0030 (13)0.0037 (11)0.0026 (11)
C30.0326 (16)0.0291 (17)0.0318 (14)0.0008 (13)0.0064 (12)0.0067 (11)
C40.0326 (16)0.0358 (18)0.0172 (13)0.0048 (11)0.0009 (12)0.0006 (10)
C50.0278 (14)0.0269 (14)0.0296 (13)0.0031 (11)0.0024 (10)0.0024 (10)
C60.0233 (14)0.0339 (16)0.0269 (12)0.0005 (11)0.0040 (10)0.0022 (12)
Geometric parameters (Å, º) top
S1—O31.453 (2)C2—C31.376 (3)
S1—O21.454 (2)C2—H20.9500
S1—O11.467 (2)C3—C41.377 (5)
S1—C11.762 (3)C3—H30.9500
C1—H1A0.9800C4—C51.382 (4)
C1—H1B0.9800C4—H40.9500
C1—H1C0.9800C5—C61.369 (4)
N1—C61.336 (4)C5—H50.9500
N1—C21.336 (4)C6—H60.9500
N1—H10.8800
O3—S1—O2113.86 (11)N1—C2—C3119.7 (4)
O3—S1—O1111.26 (13)N1—C2—H2120.2
O2—S1—O1112.23 (12)C3—C2—H2120.2
O3—S1—C1105.83 (14)C2—C3—C4119.4 (3)
O2—S1—C1106.63 (15)C2—C3—H3120.3
O1—S1—C1106.43 (12)C4—C3—H3120.3
S1—C1—H1A109.5C3—C4—C5119.5 (3)
S1—C1—H1B109.5C3—C4—H4120.2
H1A—C1—H1B109.5C5—C4—H4120.2
S1—C1—H1C109.5C6—C5—C4119.2 (3)
H1A—C1—H1C109.5C6—C5—H5120.4
H1B—C1—H1C109.5C4—C5—H5120.4
C6—N1—C2122.2 (3)N1—C6—C5120.0 (3)
C6—N1—H1118.9N1—C6—H6120.0
C2—N1—H1118.9C5—C6—H6120.0
C6—N1—C2—C30.7 (5)C3—C4—C5—C60.9 (5)
N1—C2—C3—C40.6 (6)C2—N1—C6—C50.1 (5)
C2—C3—C4—C50.2 (5)C4—C5—C6—N10.7 (5)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.881.872.730 (3)165
C4—H4···O1i0.952.483.313 (4)147
C2—H2···O2ii0.952.363.249 (4)155
C3—H3···O3ii0.952.463.288 (4)146
Symmetry codes: (i) x, y, z+1; (ii) x+3/2, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC5H6N+·CH3SO3
Mr175.20
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)173
a, b, c (Å)11.0853 (9), 8.1425 (7), 8.4530 (8)
V3)762.99 (12)
Z4
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.62 × 0.58 × 0.56
Data collection
DiffractometerSiemens CCD three-circle
diffractometer
Absorption correctionEmpirical (using intensity measurements)
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.799, 0.816
No. of measured, independent and
observed [I > 2σ(I)] reflections
7984, 1658, 1593
Rint0.033
(sin θ/λ)max1)0.672
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.098, 1.10
No. of reflections1658
No. of parameters100
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.54, 0.31
Absolute structureFlack (1983)
Absolute structure parameter0.21 (13)

Computer programs: SMART (Siemens, 1995), SMART, SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL-Plus (Sheldrick, 1991).

Selected geometric parameters (Å, º) top
S1—O31.453 (2)N1—C21.336 (4)
S1—O21.454 (2)C2—C31.376 (3)
S1—O11.467 (2)C3—C41.377 (5)
S1—C11.762 (3)C4—C51.382 (4)
N1—C61.336 (4)C5—C61.369 (4)
O3—S1—O2113.86 (11)C6—N1—C2122.2 (3)
O3—S1—O1111.26 (13)N1—C2—C3119.7 (4)
O2—S1—O1112.23 (12)C2—C3—C4119.4 (3)
O3—S1—C1105.83 (14)C3—C4—C5119.5 (3)
O2—S1—C1106.63 (15)C6—C5—C4119.2 (3)
O1—S1—C1106.43 (12)N1—C6—C5120.0 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.881.872.730 (3)164.5
C4—H4···O1i0.952.483.313 (4)146.5
C2—H2···O2ii0.952.363.249 (4)155.0
C3—H3···O3ii0.952.463.288 (4)145.8
Symmetry codes: (i) x, y, z+1; (ii) x+3/2, y1/2, z+1/2.
 

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