Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010947/cv6026sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010947/cv6026Isup2.hkl |
CCDC reference: 170894
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.002 Å
- R factor = 0.029
- wR factor = 0.079
- Data-to-parameter ratio = 22.1
checkCIF results
No syntax errors found ADDSYM reports no extra symmetry
Alert Level C:
PLAT_320 Alert C Check Hybridisation of S(1) in main residue ? General Notes
REFLT_03 From the CIF: _diffrn_reflns_theta_max 29.98 From the CIF: _reflns_number_total 1611 Count of symmetry unique reflns 958 Completeness (_total/calc) 168.16% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 653 Fraction of Friedel pairs measured 0.682 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
0 Alert Level B = Potential problem
1 Alert Level C = Please check
L-Cysteine (0.363 g, 0.003 mol) was dissolved in 2 ml of water to which 1.5 ml (0.003 mol) of 2 M HCl solution was added. 0.4 ml (0.003 mol) of 37% (w/w) formaldehyde was added. The mixture was left to react for 15 h at room temperature. Then 0.5 ml of pyridine was added. After 30 min, a white solid began to separate from the solution. Ethanol (1 ml) was added and the solution was left. Prismatic crystals separated form the solution by vacuum filtration. The crude product was recrystallized from hot water.
Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SMART; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97.
C4H7NO2S | Dx = 1.578 Mg m−3 |
Mr = 133.18 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 2816 reflections |
a = 5.6733 (3) Å | θ = 2.9–30.0° |
b = 9.9375 (6) Å | µ = 0.48 mm−1 |
c = 9.9407 (6) Å | T = 293 K |
V = 560.44 (6) Å3 | Block, colourless |
Z = 4 | 0.52 × 0.20 × 0.20 mm |
F(000) = 280 |
Bruker SMART1000 CCD diffractometer | 1611 independent reflections |
Radiation source: fine-focus sealed tube | 1483 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.027 |
ω scans | θmax = 30.0°, θmin = 2.9° |
Absorption correction: multi-scan (SADABS, Bruker, 1999) | h = −7→5 |
Tmin = 0.875, Tmax = 0.920 | k = −12→13 |
4858 measured reflections | l = −13→13 |
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)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.079 | w = 1/[σ2(Fo2) + (0.053P)2P] where P = (Fo2 + 2Fc2)/3 |
S = 1.03 | (Δ/σ)max < 0.001 |
1611 reflections | Δρmax = 0.28 e Å−3 |
73 parameters | Δρmin = −0.23 e Å−3 |
0 restraints | Absolute structure: (Flack, 1983) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.07 (8) |
C4H7NO2S | V = 560.44 (6) Å3 |
Mr = 133.18 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.6733 (3) Å | µ = 0.48 mm−1 |
b = 9.9375 (6) Å | T = 293 K |
c = 9.9407 (6) Å | 0.52 × 0.20 × 0.20 mm |
Bruker SMART1000 CCD diffractometer | 1611 independent reflections |
Absorption correction: multi-scan (SADABS, Bruker, 1999) | 1483 reflections with I > 2σ(I) |
Tmin = 0.875, Tmax = 0.920 | Rint = 0.027 |
4858 measured reflections |
R[F2 > 2σ(F2)] = 0.029 | H-atom parameters constrained |
wR(F2) = 0.079 | Δρmax = 0.28 e Å−3 |
S = 1.03 | Δρmin = −0.23 e Å−3 |
1611 reflections | Absolute structure: (Flack, 1983) |
73 parameters | Absolute structure parameter: 0.07 (8) |
0 restraints |
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 | 0.10887 (7) | 0.17235 (4) | 0.38298 (4) | 0.03733 (12) | |
O1 | −0.27669 (19) | −0.00443 (12) | 0.11609 (14) | 0.0360 (2) | |
N1 | 0.3165 (2) | 0.12326 (12) | 0.15031 (11) | 0.0250 (2) | |
H1A | 0.4381 | 0.0932 | 0.1251 | 0.030* | |
H1B | 0.2707 | 0.1723 | 0.0909 | 0.030* | |
O2 | −0.0738 (2) | 0.15571 (15) | 0.00960 (14) | 0.0487 (3) | |
C1 | −0.0948 (2) | 0.06210 (14) | 0.09099 (13) | 0.0258 (3) | |
C2 | 0.1292 (2) | 0.01851 (13) | 0.16804 (12) | 0.0225 (2) | |
H2 | 0.1858 | −0.0671 | 0.1311 | 0.027* | |
C3 | 0.0883 (3) | 0.00246 (16) | 0.31848 (14) | 0.0319 (3) | |
H3A | 0.2077 | −0.0549 | 0.3585 | 0.038* | |
H3B | −0.0659 | −0.0357 | 0.3363 | 0.038* | |
C4 | 0.3628 (3) | 0.19746 (15) | 0.27834 (15) | 0.0337 (3) | |
H4A | 0.3858 | 0.2925 | 0.2605 | 0.040* | |
H4B | 0.5030 | 0.1626 | 0.3220 | 0.040* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0374 (2) | 0.0440 (2) | 0.03060 (16) | 0.00468 (17) | 0.00258 (16) | −0.00600 (16) |
O1 | 0.0193 (5) | 0.0357 (5) | 0.0532 (6) | −0.0010 (4) | −0.0035 (5) | 0.0079 (6) |
N1 | 0.0179 (5) | 0.0280 (5) | 0.0292 (5) | 0.0000 (4) | −0.0001 (4) | 0.0043 (5) |
O2 | 0.0316 (6) | 0.0568 (8) | 0.0575 (7) | −0.0026 (6) | −0.0126 (5) | 0.0315 (7) |
C1 | 0.0198 (6) | 0.0278 (6) | 0.0299 (6) | 0.0032 (5) | −0.0016 (5) | 0.0006 (5) |
C2 | 0.0173 (5) | 0.0221 (5) | 0.0279 (5) | 0.0015 (5) | 0.0000 (5) | 0.0014 (5) |
C3 | 0.0329 (8) | 0.0331 (7) | 0.0296 (6) | −0.0033 (6) | −0.0022 (6) | 0.0100 (5) |
C4 | 0.0305 (7) | 0.0321 (7) | 0.0386 (7) | −0.0048 (6) | −0.0020 (6) | −0.0056 (6) |
S1—C4 | 1.7945 (16) | C1—C2 | 1.5457 (18) |
S1—C3 | 1.8097 (17) | C2—C3 | 1.5217 (19) |
O1—C1 | 1.2509 (18) | C2—H2 | 0.9800 |
N1—C4 | 1.4942 (18) | C3—H3A | 0.9700 |
N1—C2 | 1.4978 (17) | C3—H3B | 0.9700 |
N1—H1A | 0.7924 | C4—H4A | 0.9700 |
N1—H1B | 0.8087 | C4—H4B | 0.9700 |
O2—C1 | 1.2386 (18) | ||
C4—S1—C3 | 88.62 (7) | C3—C2—H2 | 109.1 |
C4—N1—C2 | 111.56 (10) | C1—C2—H2 | 109.1 |
C4—N1—H1A | 107.6 | C2—C3—S1 | 103.92 (9) |
C2—N1—H1A | 113.1 | C2—C3—H3A | 111.0 |
C4—N1—H1B | 112.4 | S1—C3—H3A | 111.0 |
C2—N1—H1B | 106.1 | C2—C3—H3B | 111.0 |
H1A—N1—H1B | 106.0 | S1—C3—H3B | 111.0 |
O2—C1—O1 | 127.34 (13) | H3A—C3—H3B | 109.0 |
O2—C1—C2 | 117.08 (12) | N1—C4—S1 | 106.49 (9) |
O1—C1—C2 | 115.56 (12) | N1—C4—H4A | 110.4 |
N1—C2—C3 | 107.25 (11) | S1—C4—H4A | 110.4 |
N1—C2—C1 | 109.28 (10) | N1—C4—H4B | 110.4 |
C3—C2—C1 | 113.02 (12) | S1—C4—H4B | 110.4 |
N1—C2—H2 | 109.1 | H4A—C4—H4B | 108.6 |
O2—C1—C2—N1 | 13.51 (18) | N1—C4—S1—C3 | 36.89 (10) |
O2—C1—C2—C3 | 132.85 (15) | C4—S1—C3—C2 | −43.76 (11) |
O1—C1—C2—N1 | −168.24 (12) | S1—C3—C2—N1 | 38.68 (13) |
O1—C1—C2—N1 | −168.24 (12) | C3—C2—N1—C4 | −12.38 (15) |
C2—N1—C4—S1 | −19.86 (13) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.79 | 1.89 | 2.6556 (16) | 163 |
N1—H1B···O2 | 0.81 | 2.12 | 2.6389 (16) | 122 |
N1—H1B···O2ii | 0.81 | 2.17 | 2.7819 (16) | 133 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z. |
Experimental details
Crystal data | |
Chemical formula | C4H7NO2S |
Mr | 133.18 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 5.6733 (3), 9.9375 (6), 9.9407 (6) |
V (Å3) | 560.44 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.48 |
Crystal size (mm) | 0.52 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART1000 CCD diffractometer |
Absorption correction | Multi-scan (SADABS, Bruker, 1999) |
Tmin, Tmax | 0.875, 0.920 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4858, 1611, 1483 |
Rint | 0.027 |
(sin θ/λ)max (Å−1) | 0.703 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.029, 0.079, 1.03 |
No. of reflections | 1611 |
No. of parameters | 73 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.28, −0.23 |
Absolute structure | (Flack, 1983) |
Absolute structure parameter | 0.07 (8) |
Computer programs: SMART (Bruker, 1999), SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.
S1—C4 | 1.7945 (16) | N1—C2 | 1.4978 (17) |
S1—C3 | 1.8097 (17) | O2—C1 | 1.2386 (18) |
O1—C1 | 1.2509 (18) | C1—C2 | 1.5457 (18) |
N1—C4 | 1.4942 (18) | C2—C3 | 1.5217 (19) |
C4—S1—C3 | 88.62 (7) | N1—C2—C3 | 107.25 (11) |
C4—N1—C2 | 111.56 (10) | N1—C2—C1 | 109.28 (10) |
O2—C1—O1 | 127.34 (13) | C3—C2—C1 | 113.02 (12) |
O2—C1—C2 | 117.08 (12) | C2—C3—S1 | 103.92 (9) |
O1—C1—C2 | 115.56 (12) | N1—C4—S1 | 106.49 (9) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1i | 0.79 | 1.89 | 2.6556 (16) | 162.6 |
N1—H1B···O2 | 0.81 | 2.12 | 2.6389 (16) | 121.8 |
N1—H1B···O2ii | 0.81 | 2.17 | 2.7819 (16) | 132.9 |
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, −y+1/2, −z. |
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(R)-1,3-Thiazolidin-3-ium-4-carboxylate, (I), was prepared as part of our studies into synthetic routes to derivatives of the potent cytotoxic agent thiocoraline (Boger et al., 2001).
The non-H-atom geometrical parameters are normal and are determined to higher precision than those arising from the earlier studies on the natural S-form of thioproline (Loscalzo et al., 1973; Chacko, 1974). There was some ambiguity in these studies as to the location of the transferrable (carboxyl/amino) proton. The small C—S—C bond angle is comparable to that seen in other thiazoladine derivatives (Gainsford et al., 1980). The absolute structure (R chirality of C2) of the title compound is consistent with that of the L-cysteine starting material.
This work unambiguously shows that a zwitterion is present in the crystal. The two N—H entities interact with both carboxyl oxygen species (Table 2) resulting in a one-dimensional network of hydrogen bonds propagating in the [100] direction (Fig. 3). The N1—H1B moiety is involved in bifurcated hydrogen bonding, one link being intramolecular, the other intermolecular. There are no significant sulfur–sulfur interactions [shortest S···Si contact = 3.981 (1) Å; symmetry code: (i) 1/2 + x, 1/2 - y, 1 - z].