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The title compound, synthetic (R)-thio­proline, C4H7NO2S, crystallizes from water as a zwitterion. The N—H...O hydrogen-bonding scheme involves both intra- and intermolecular interactions.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536801010947/cv6026sup1.cif
Contains datablocks I, neil

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536801010947/cv6026Isup2.hkl
Contains datablock I

CCDC reference: 170894

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

(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].

Experimental top

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.

Computing details top

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.

Figures top
[Figure 1] Fig. 1. The structure of (I) (50% displacement ellipsoids, arbitrary spheres for the H atoms).
[Figure 2] Fig. 2. Packing diagram for (I).
[Figure 3] Fig. 3. Hydrogen-bonding scheme in (I). Symmetry codes are as in Table 2.
(R)-1,3-Thiazolidin-3-ium-4-carboxylate top
Crystal data top
C4H7NO2SDx = 1.578 Mg m3
Mr = 133.18Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P212121Cell parameters from 2816 reflections
a = 5.6733 (3) Åθ = 2.9–30.0°
b = 9.9375 (6) ŵ = 0.48 mm1
c = 9.9407 (6) ÅT = 293 K
V = 560.44 (6) Å3Block, colourless
Z = 40.52 × 0.20 × 0.20 mm
F(000) = 280
Data collection top
Bruker SMART1000 CCD
diffractometer
1611 independent reflections
Radiation source: fine-focus sealed tube1483 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.027
ω scansθmax = 30.0°, θmin = 2.9°
Absorption correction: multi-scan
(SADABS, Bruker, 1999)
h = 75
Tmin = 0.875, Tmax = 0.920k = 1213
4858 measured reflectionsl = 1313
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)] = 0.029H-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 reflectionsΔρmax = 0.28 e Å3
73 parametersΔρmin = 0.23 e Å3
0 restraintsAbsolute structure: (Flack, 1983)
Primary atom site location: structure-invariant direct methodsAbsolute structure parameter: 0.07 (8)
Crystal data top
C4H7NO2SV = 560.44 (6) Å3
Mr = 133.18Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 5.6733 (3) ŵ = 0.48 mm1
b = 9.9375 (6) ÅT = 293 K
c = 9.9407 (6) Å0.52 × 0.20 × 0.20 mm
Data collection top
Bruker SMART1000 CCD
diffractometer
1611 independent reflections
Absorption correction: multi-scan
(SADABS, Bruker, 1999)
1483 reflections with I > 2σ(I)
Tmin = 0.875, Tmax = 0.920Rint = 0.027
4858 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.029H-atom parameters constrained
wR(F2) = 0.079Δρmax = 0.28 e Å3
S = 1.03Δρmin = 0.23 e Å3
1611 reflectionsAbsolute structure: (Flack, 1983)
73 parametersAbsolute structure parameter: 0.07 (8)
0 restraints
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
S10.10887 (7)0.17235 (4)0.38298 (4)0.03733 (12)
O10.27669 (19)0.00443 (12)0.11609 (14)0.0360 (2)
N10.3165 (2)0.12326 (12)0.15031 (11)0.0250 (2)
H1A0.43810.09320.12510.030*
H1B0.27070.17230.09090.030*
O20.0738 (2)0.15571 (15)0.00960 (14)0.0487 (3)
C10.0948 (2)0.06210 (14)0.09099 (13)0.0258 (3)
C20.1292 (2)0.01851 (13)0.16804 (12)0.0225 (2)
H20.18580.06710.13110.027*
C30.0883 (3)0.00246 (16)0.31848 (14)0.0319 (3)
H3A0.20770.05490.35850.038*
H3B0.06590.03570.33630.038*
C40.3628 (3)0.19746 (15)0.27834 (15)0.0337 (3)
H4A0.38580.29250.26050.040*
H4B0.50300.16260.32200.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0374 (2)0.0440 (2)0.03060 (16)0.00468 (17)0.00258 (16)0.00600 (16)
O10.0193 (5)0.0357 (5)0.0532 (6)0.0010 (4)0.0035 (5)0.0079 (6)
N10.0179 (5)0.0280 (5)0.0292 (5)0.0000 (4)0.0001 (4)0.0043 (5)
O20.0316 (6)0.0568 (8)0.0575 (7)0.0026 (6)0.0126 (5)0.0315 (7)
C10.0198 (6)0.0278 (6)0.0299 (6)0.0032 (5)0.0016 (5)0.0006 (5)
C20.0173 (5)0.0221 (5)0.0279 (5)0.0015 (5)0.0000 (5)0.0014 (5)
C30.0329 (8)0.0331 (7)0.0296 (6)0.0033 (6)0.0022 (6)0.0100 (5)
C40.0305 (7)0.0321 (7)0.0386 (7)0.0048 (6)0.0020 (6)0.0056 (6)
Geometric parameters (Å, º) top
S1—C41.7945 (16)C1—C21.5457 (18)
S1—C31.8097 (17)C2—C31.5217 (19)
O1—C11.2509 (18)C2—H20.9800
N1—C41.4942 (18)C3—H3A0.9700
N1—C21.4978 (17)C3—H3B0.9700
N1—H1A0.7924C4—H4A0.9700
N1—H1B0.8087C4—H4B0.9700
O2—C11.2386 (18)
C4—S1—C388.62 (7)C3—C2—H2109.1
C4—N1—C2111.56 (10)C1—C2—H2109.1
C4—N1—H1A107.6C2—C3—S1103.92 (9)
C2—N1—H1A113.1C2—C3—H3A111.0
C4—N1—H1B112.4S1—C3—H3A111.0
C2—N1—H1B106.1C2—C3—H3B111.0
H1A—N1—H1B106.0S1—C3—H3B111.0
O2—C1—O1127.34 (13)H3A—C3—H3B109.0
O2—C1—C2117.08 (12)N1—C4—S1106.49 (9)
O1—C1—C2115.56 (12)N1—C4—H4A110.4
N1—C2—C3107.25 (11)S1—C4—H4A110.4
N1—C2—C1109.28 (10)N1—C4—H4B110.4
C3—C2—C1113.02 (12)S1—C4—H4B110.4
N1—C2—H2109.1H4A—C4—H4B108.6
O2—C1—C2—N113.51 (18)N1—C4—S1—C336.89 (10)
O2—C1—C2—C3132.85 (15)C4—S1—C3—C243.76 (11)
O1—C1—C2—N1168.24 (12)S1—C3—C2—N138.68 (13)
O1—C1—C2—N1168.24 (12)C3—C2—N1—C412.38 (15)
C2—N1—C4—S119.86 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.791.892.6556 (16)163
N1—H1B···O20.812.122.6389 (16)122
N1—H1B···O2ii0.812.172.7819 (16)133
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC4H7NO2S
Mr133.18
Crystal system, space groupOrthorhombic, P212121
Temperature (K)293
a, b, c (Å)5.6733 (3), 9.9375 (6), 9.9407 (6)
V3)560.44 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.48
Crystal size (mm)0.52 × 0.20 × 0.20
Data collection
DiffractometerBruker SMART1000 CCD
diffractometer
Absorption correctionMulti-scan
(SADABS, Bruker, 1999)
Tmin, Tmax0.875, 0.920
No. of measured, independent and
observed [I > 2σ(I)] reflections
4858, 1611, 1483
Rint0.027
(sin θ/λ)max1)0.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.029, 0.079, 1.03
No. of reflections1611
No. of parameters73
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.28, 0.23
Absolute structure(Flack, 1983)
Absolute structure parameter0.07 (8)

Computer programs: SMART (Bruker, 1999), SMART, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-3 (Farrugia, 1997), SHELXL97.

Selected geometric parameters (Å, º) top
S1—C41.7945 (16)N1—C21.4978 (17)
S1—C31.8097 (17)O2—C11.2386 (18)
O1—C11.2509 (18)C1—C21.5457 (18)
N1—C41.4942 (18)C2—C31.5217 (19)
C4—S1—C388.62 (7)N1—C2—C3107.25 (11)
C4—N1—C2111.56 (10)N1—C2—C1109.28 (10)
O2—C1—O1127.34 (13)C3—C2—C1113.02 (12)
O2—C1—C2117.08 (12)C2—C3—S1103.92 (9)
O1—C1—C2115.56 (12)N1—C4—S1106.49 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O1i0.791.892.6556 (16)162.6
N1—H1B···O20.812.122.6389 (16)121.8
N1—H1B···O2ii0.812.172.7819 (16)132.9
Symmetry codes: (i) x+1, y, z; (ii) x+1/2, y+1/2, z.
 

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