Redetermination of 1,3-thia­zolidine-2,4-dione

Lynch, D.E.; McClenaghan, I.; Light, M.E.

doi:10.1107/S1600536800020717

Redetermination of 1,3-thiazolidine-2,4-dione

D. E. Lynch, I. McClenaghan and M. E. Light

The structure of the title compound, C₃H₃NO₂S, comprises flat molecules that associate via a single N—H

O interaction and a C—H

O close contact to the second O atom. Furthermore, 10% of the molecules have S and CH₂ interchanged, generating disorder.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536800020717/cf6032sup1.cif Contains datablocks I, default
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536800020717/cf6032Isup2.hkl Contains datablock I

CCDC reference: 155898

checkCIF report

Key indicators

Single-crystal X-ray study
T = 150 K
Mean () = 0.000 Å
Disorder in solvent or counterion
R factor = 0.031
wR factor = 0.083
Data-to-parameter ratio = 14.5

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry


 Alert Level C:



PLAT_302  Alert C Anion/Solvent disorder .......................      50.00 Perc.


 0 Alert Level A = Potentially serious problem

 0 Alert Level B = Potential problem

 1 Alert Level C = Please check

Comment top

The structure of the title compound, (I), is known with the room-temperature structure being refined to R = 0.069 (Form et al., 1975). Refinement on data collected at 150 K yielded R = 0.066 but left C5 as non-positive-definite, with significant electron density close to this atom. Further refinement of the disorder revealed that 10% of the molecules have S and CH₂ interchanged, with the O═C—NH—C═O sites being in common. The molecule was consequently split into two separate partial-occupancy fragments and refined in both configurations with bond distances (for the major fragment) allowed to vary while the displacement parameters and ring geometry were restrained to be equal in each portion.

Experimental top

The title compound, (I), was prepared by Spa Contract Synthesis.

Computing details top

Data collection: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998); cell refinement: DENZO and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. The molecular configuration and atom numbering scheme for (I), showing 50% probability displacement ellipsoids.

Thiazolidine-2,4-dione top

Crystal data top

C₃H₃NO₂S	D_x = 1.736 Mg m⁻³
M_r = 117.12	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, Pbca	Cell parameters from 3675 reflections
a = 7.2926 (2) Å	θ = 1.0–27.5°
b = 9.3642 (3) Å	µ = 0.58 mm⁻¹
c = 13.1208 (5) Å	T = 150 K
V = 896.01 (5) Å³	Plate, colourless
Z = 8	0.50 × 0.30 × 0.07 mm
F(000) = 480

Data collection top

Enraf Nonius KappaCCD area-detector diffractometer	1018 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode	919 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.057
Detector resolution: 9.091 pixels mm^-1	θ_max = 27.5°, θ_min = 3.9°
ϕ and ω scans	h = −9→9
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	k = −12→12
T_min = 0.759, T_max = 0.960	l = −16→17
5895 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.083	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0403P)² + 0.44P] where P = (F_o² + 2F_c²)/3
1018 reflections	(Δ/σ)_max < 0.001
70 parameters	Δρ_max = 0.37 e Å⁻³
6 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₃H₃NO₂S	V = 896.01 (5) Å³
M_r = 117.12	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 7.2926 (2) Å	µ = 0.58 mm⁻¹
b = 9.3642 (3) Å	T = 150 K
c = 13.1208 (5) Å	0.50 × 0.30 × 0.07 mm

Data collection top

Enraf Nonius KappaCCD area-detector diffractometer	1018 independent reflections
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	919 reflections with I > 2σ(I)
T_min = 0.759, T_max = 0.960	R_int = 0.057
5895 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	6 restraints
wR(F²) = 0.083	H-atom parameters constrained
S = 1.09	Δρ_max = 0.37 e Å⁻³
1018 reflections	Δρ_min = −0.29 e Å⁻³
70 parameters

Special details top

Experimental. PLEASE NOTE cell_measurement_ fields are not relevant to area detector data, the entire data set is used to refine the cell, which is indexed from all observed reflections in a 10 degree phi range.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq	Occ. (<1)
S1A	0.11671 (13)	0.12963 (6)	0.40807 (5)	0.01904 (17)	0.90
C2A	0.07455 (19)	0.29840 (15)	0.46006 (10)	0.0170 (3)	0.90
O21A	0.13631 (15)	0.33939 (12)	0.54147 (8)	0.0241 (3)	0.90
N3A	−0.03733 (17)	0.37873 (12)	0.39882 (9)	0.0162 (3)	0.90
H3A	−0.0701	0.4658	0.4163	0.019*	0.90
C4A	−0.09631 (18)	0.31872 (15)	0.30949 (11)	0.0174 (3)	0.90
O41A	−0.19474 (17)	0.37952 (10)	0.24901 (9)	0.0254 (3)	0.90
C5A	−0.0243 (6)	0.1692 (2)	0.2950 (3)	0.0165 (4)	0.90
H51A	0.0507	0.1632	0.2323	0.020*	0.90
H52A	−0.1269	0.1004	0.2895	0.020*	0.90
S1B	−0.0163 (17)	0.1465 (7)	0.2928 (7)	0.01904 (17)	0.10
C2B	0.07455 (19)	0.29840 (15)	0.46006 (10)	0.0170 (3)	0.10
O21B	0.13631 (15)	0.33939 (12)	0.54147 (8)	0.0241 (3)	0.10
N3B	−0.03733 (17)	0.37873 (12)	0.39882 (9)	0.0162 (3)	0.10
H3B	−0.0701	0.4658	0.4163	0.019*	0.10
C4B	−0.09631 (18)	0.31872 (15)	0.30949 (11)	0.0174 (3)	0.10
O41B	−0.19474 (17)	0.37952 (10)	0.24901 (9)	0.0254 (3)	0.10
C5B	0.108 (5)	0.1525 (18)	0.4151 (18)	0.0165 (4)	0.10
H51B	0.0624	0.0773	0.4617	0.020*	0.10
H52B	0.2411	0.1373	0.4040	0.020*	0.10

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1A	0.0213 (3)	0.0135 (3)	0.0223 (3)	0.0033 (2)	−0.00173 (18)	−0.00065 (16)
C2A	0.0158 (6)	0.0150 (6)	0.0204 (7)	0.0008 (5)	0.0019 (5)	0.0005 (5)
O21A	0.0283 (6)	0.0211 (5)	0.0229 (6)	0.0063 (5)	−0.0061 (4)	−0.0029 (4)
N3A	0.0161 (6)	0.0120 (6)	0.0206 (6)	0.0013 (4)	−0.0010 (5)	−0.0015 (4)
C4A	0.0142 (7)	0.0154 (7)	0.0226 (7)	−0.0031 (5)	−0.0002 (5)	0.0000 (5)
O41A	0.0272 (6)	0.0193 (5)	0.0298 (6)	0.0001 (4)	−0.0112 (5)	0.0001 (4)
C5A	0.0141 (9)	0.0088 (12)	0.0266 (8)	0.0017 (10)	−0.0012 (7)	0.0026 (9)
S1B	0.0213 (3)	0.0135 (3)	0.0223 (3)	0.0033 (2)	−0.00173 (18)	−0.00065 (16)
C2B	0.0158 (6)	0.0150 (6)	0.0204 (7)	0.0008 (5)	0.0019 (5)	0.0005 (5)
O21B	0.0283 (6)	0.0211 (5)	0.0229 (6)	0.0063 (5)	−0.0061 (4)	−0.0029 (4)
N3B	0.0161 (6)	0.0120 (6)	0.0206 (6)	0.0013 (4)	−0.0010 (5)	−0.0015 (4)
C4B	0.0142 (7)	0.0154 (7)	0.0226 (7)	−0.0031 (5)	−0.0002 (5)	0.0000 (5)
O41B	0.0272 (6)	0.0193 (5)	0.0298 (6)	0.0001 (4)	−0.0112 (5)	0.0001 (4)
C5B	0.0141 (9)	0.0088 (12)	0.0266 (8)	0.0017 (10)	−0.0012 (7)	0.0026 (9)

Geometric parameters (Å, º) top

S1A—C2A	1.7485 (15)	C5A—S1A	1.842 (3)
O21A—C2A	1.2212 (18)	C5A—H51A	0.99
N3A—C2A	1.3701 (18)	C5A—H52A	0.99
N3A—C4A	1.3691 (18)	C5B—S1B	1.846 (5)
N3A—H3A	0.88	C5B—H51B	0.99
C4A—C5A	1.508 (2)	C5B—H52B	0.99
O41A—C4A	1.2120 (18)

C4A—N3A—C2A	117.63 (12)	S1A—C5A—H52A	110.5
C4A—N3A—H3A	121.2	H51A—C5A—H52A	108.7
C2A—N3A—H3A	121.2	C2A—S1A—C5A	91.96 (8)
O41A—C4A—N3A	123.62 (13)	O21A—C2A—N3A	124.06 (13)
O41A—C4A—C5A	124.08 (17)	O21A—C2A—S1A	124.09 (11)
N3A—C4A—C5A	112.29 (17)	N3A—C2A—S1A	111.85 (10)
C4A—C5A—S1A	106.27 (17)	S1B—C5B—H51B	110.4
C4A—C5A—H51A	110.5	S1B—C5B—H52B	110.4
S1A—C5A—H51A	110.5	H51B—C5B—H52B	108.6
C4A—C5A—H52A	110.5

C2A—N3A—C4A—O41A	−179.62 (14)	C4A—N3A—C2A—O21A	−179.98 (13)
C2A—N3A—C4A—C5A	0.2 (3)	C4A—N3A—C2A—S1A	−0.46 (16)
O41A—C4A—C5A—S1A	179.97 (17)	C5A—S1A—C2A—O21A	180.0 (2)
N3A—C4A—C5A—S1A	0.2 (3)	C5A—S1A—C2A—N3A	0.5 (2)
C4A—C5A—S1A—C2A	−0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3A—H3A···O21Aⁱ	0.88	1.97	2.8465 (16)	178
C5A—H52A···O41Aⁱⁱ	0.99	2.50	3.453 (3)	161

Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x−1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₃H₃NO₂S
M_r	117.12
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	150
a, b, c (Å)	7.2926 (2), 9.3642 (3), 13.1208 (5)
V (Å³)	896.01 (5)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.58
Crystal size (mm)	0.50 × 0.30 × 0.07

Data collection
Diffractometer	Enraf Nonius KappaCCD area-detector diffractometer
Absorption correction	Multi-scan (SORTAV; Blessing, 1995)
T_min, T_max	0.759, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	5895, 1018, 919
R_int	0.057
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.083, 1.09
No. of reflections	1018
No. of parameters	70
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.29

Computer programs: DENZO (Otwinowski & Minor, 1997) and COLLECT (Hooft, 1998), DENZO and COLLECT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXL97.