(Z)-5-(4-Fluoro­benzyl­idene)-1,3-thia­zolidine-2,4-dione

Sun, H.-S.; Xu, Y.-M.; He, W.; Tang, S.-G.; Guo, C.

doi:10.1107/S1600536807068316

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 2| February 2008| Page o524

doi:10.1107/S1600536807068316

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(Z)-5-(4-Fluorobenzylidene)-1,3-thiazolidine-2,4-dione

Hong-Shun Sun,^a Ye-Ming Xu,^a Wei He,^a Shi-Gui Tang ^a and Cheng Guo ^a ^*

^aDepartment of Applied Chemistry, College of Sciences, Nanjing University of Technolgy, Xinmofan Road No. 5, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: guocheng@njut.edu.cn

(Received 30 November 2007; accepted 24 December 2007; online 25 January 2008)

In the title compound, C₁₀H₆FNO₂S, the benzene and thiazolidine rings make a dihedral angle of 7.52 (3)°. Intramolecular C—H⋯O and C—H⋯S hydrogen bonds result in the formation of nearly planar five- and six-membered rings; the adjacent rings are nearly coplanar. In the crystal structure, intermolecular N—H⋯O hydrogen bonds link the molecules.

Related literature

For general background, see: Barreca et al. (2002 ); Botti et al. (1996 ). For a related structure, see: Guo et al. (2006 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₆FNO₂S
M_r = 223.22
Orthorhombic, F d d 2
a = 26.519 (5) Å
b = 36.509 (7) Å
c = 3.8490 (8) Å
V = 3726.6 (13) Å³
Z = 16
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 294 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.905, T_max = 0.967
2087 measured reflections
1059 independent reflections
790 reflections with I > 2σ(I)
R_int = 0.042
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.121
S = 1.04
1059 reflections
136 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.66 e Å⁻³
Absolute structure: Flack (1983 ), no Friedel pairs
Flack parameter: 0.0 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N—H0A⋯O2ⁱ	0.86	1.98	2.830 (5)	171
C5—H5A⋯S	0.93	2.54	3.241 (5)	133
C7—H7A⋯O2	0.93	2.50	2.870 (5)	104
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y, z-{\script{1\over 2}}]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Siemens, 1996 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807068316/hk2407sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536807068316/hk2407Isup2.hkl

checkCIF report

Comment top

Thiazolidines are an important class of heteroaromatic compounds and have widespread applications from pharmaceuticals (Barreca et al., 2002) to materials (Botti et al., 1996). As part of our ongoing studies in this area (Guo et al., 2006), we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···O and C—H···S hydrogen bonds (Table 1) result in the formations of nearly planar five- and six-membered rings; C (S/H5A/C4/C5/C7/C8) and D (O2/H7A/C7—C9). Rings A (C1—C6) and B (N/S/C8—C10) are, of course, planar and the dihedral angles between them are A/B = 7.52 (3)°, A/C = 4.73 (3)°, A/D = 6.90 (3)°, B/C = 3.63 (2)°, B/D = 2.39 (3)° and C/D = 4.56 (2)°. So, the adjacent rings are also nearly co-planar.

In the crystal structure, intermolecular N—H···O hydrogen bonds (Table 1) link the molecules, in which they may be effective in the stabilization of the structure.

Related literature top

For general background, see: Barreca et al. (2002); Botti et al. (1996). For a related structure, see: Guo et al. (2006). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, thiazolidine-2,4-dione (10 mmol) and 4-fluorobenzaldehyde (10 mmol) were dissolved in ethanol (10 ml) in a round-bottomed flask (50 ml) and 5 drops of piperidine were added. The flask was heated in a modified domestic microwave oven at 300 W for 5 min. After cooling, the mixture was poured into water and the crude compound (I) filtered out. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bonds are shown as dashed lines.

(Z)-5-(4-Fluorobenzylidene)-1,3-thiazolidine-2,4-dione top

Crystal data top

C₁₀H₆FNO₂S	F(000) = 1824
M_r = 223.22	D_x = 1.591 Mg m⁻³
Orthorhombic, Fdd2	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2d	Cell parameters from 25 reflections
a = 26.519 (5) Å	θ = 9–13°
b = 36.509 (7) Å	µ = 0.34 mm⁻¹
c = 3.8490 (8) Å	T = 294 K
V = 3726.6 (13) Å³	Block, colorles
Z = 16	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	790 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 26.0°, θ_min = 1.9°
ω/2θ scans	h = 0→32
Absorption correction: ψ scan (North et al., 1968)	k = 0→44
T_min = 0.905, T_max = 0.967	l = −4→0
2087 measured reflections	3 standard reflections every 120 min
1059 independent reflections	intensity decay: none

Refinement top

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)] = 0.053	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.05P)² + 3P] where P = (F_o² + 2F_c²)/3
S = 1.04	(Δ/σ)_max < 0.001
1059 reflections	Δρ_max = 0.38 e Å⁻³
136 parameters	Δρ_min = −0.66 e Å⁻³
1 restraint	Absolute structure: Flack (1983), no Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.0 (2)

Crystal data top

C₁₀H₆FNO₂S	V = 3726.6 (13) Å³
M_r = 223.22	Z = 16
Orthorhombic, Fdd2	Mo Kα radiation
a = 26.519 (5) Å	µ = 0.34 mm⁻¹
b = 36.509 (7) Å	T = 294 K
c = 3.8490 (8) Å	0.30 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	790 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.905, T_max = 0.967	3 standard reflections every 120 min
2087 measured reflections	intensity decay: none
1059 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.121	Δρ_max = 0.38 e Å⁻³
S = 1.04	Δρ_min = −0.66 e Å⁻³
1059 reflections	Absolute structure: Flack (1983), no Friedel pairs
136 parameters	Absolute structure parameter: 0.0 (2)
1 restraint

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

	x	y	z	U_iso*/U_eq
S	0.08943 (4)	−0.00189 (3)	−0.0089 (5)	0.0379 (3)
F	−0.06109 (11)	0.13395 (8)	0.6207 (12)	0.0681 (12)
O1	0.13745 (13)	−0.05739 (9)	−0.3062 (14)	0.0619 (12)
O2	0.21942 (10)	0.03754 (8)	0.2142 (14)	0.0493 (10)
N	0.18501 (14)	−0.01228 (9)	−0.0627 (14)	0.0425 (11)
H0A	0.2136	−0.0219	−0.1150	0.051*
C1	−0.01787 (17)	0.11646 (12)	0.5430 (15)	0.0416 (12)
C2	0.02675 (18)	0.13443 (12)	0.5921 (16)	0.0484 (15)
H2A	0.0273	0.1584	0.6744	0.058*
C3	0.07078 (19)	0.11621 (11)	0.5166 (17)	0.0444 (13)
H3A	0.1015	0.1278	0.5559	0.053*
C4	0.07035 (16)	0.08082 (10)	0.3826 (13)	0.0346 (11)
C5	0.02378 (16)	0.06382 (12)	0.3314 (15)	0.0400 (12)
H5A	0.0225	0.0402	0.2421	0.048*
C6	−0.02016 (15)	0.08195 (12)	0.4125 (16)	0.0452 (14)
H6A	−0.0512	0.0707	0.3782	0.054*
C7	0.11827 (16)	0.06366 (11)	0.3095 (14)	0.0352 (10)
H7A	0.1462	0.0772	0.3782	0.042*
C8	0.12929 (15)	0.03151 (11)	0.1597 (14)	0.0317 (10)
C9	0.18224 (17)	0.02026 (11)	0.1107 (15)	0.0370 (12)
C10	0.14053 (17)	−0.02927 (12)	−0.1510 (17)	0.0450 (13)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.0303 (5)	0.0391 (5)	0.0444 (6)	−0.0005 (4)	0.0015 (7)	−0.0028 (6)
F	0.0400 (16)	0.0705 (18)	0.094 (3)	0.0212 (14)	0.003 (2)	−0.024 (2)
O1	0.058 (2)	0.0465 (17)	0.081 (3)	0.0105 (16)	0.000 (3)	−0.026 (2)
O2	0.0267 (16)	0.0444 (16)	0.077 (3)	0.0002 (12)	−0.0039 (19)	0.001 (2)
N	0.0295 (18)	0.0403 (18)	0.058 (3)	0.0068 (15)	0.001 (2)	0.001 (2)
C1	0.033 (2)	0.051 (2)	0.041 (3)	0.012 (2)	0.003 (2)	−0.009 (3)
C2	0.047 (3)	0.042 (2)	0.056 (4)	0.012 (2)	−0.009 (3)	−0.018 (3)
C3	0.047 (3)	0.036 (2)	0.050 (3)	−0.0028 (19)	−0.002 (3)	−0.007 (3)
C4	0.031 (2)	0.036 (2)	0.036 (3)	0.0030 (17)	−0.002 (2)	−0.002 (2)
C5	0.035 (2)	0.038 (2)	0.047 (3)	0.0012 (17)	−0.001 (2)	−0.006 (2)
C6	0.0209 (18)	0.056 (3)	0.058 (4)	−0.0019 (18)	0.007 (2)	−0.018 (3)
C7	0.030 (2)	0.042 (2)	0.033 (3)	−0.0057 (17)	0.000 (2)	0.008 (2)
C8	0.024 (2)	0.040 (2)	0.031 (3)	0.0007 (16)	−0.003 (2)	0.009 (2)
C9	0.032 (2)	0.037 (2)	0.042 (3)	0.0039 (18)	−0.001 (2)	0.011 (2)
C10	0.038 (2)	0.042 (2)	0.055 (4)	0.0065 (19)	−0.002 (3)	0.002 (3)

Geometric parameters (Å, º) top

S—C8	1.739 (4)	C2—H2A	0.9300
S—C10	1.770 (5)	C3—C4	1.391 (6)
F—C1	1.346 (5)	C3—H3A	0.9300
O1—C10	1.191 (6)	C4—C5	1.396 (6)
O2—C9	1.237 (5)	C4—C7	1.445 (6)
N—C9	1.364 (6)	C5—C6	1.376 (6)
N—C10	1.375 (6)	C5—H5A	0.9300
N—H0A	0.8600	C6—H6A	0.9300
C1—C6	1.358 (6)	C7—C8	1.340 (6)
C1—C2	1.366 (7)	C7—H7A	0.9300
C2—C3	1.375 (6)	C8—C9	1.475 (6)

C8—S—C10	92.6 (2)	C6—C5—H5A	119.9
C9—N—C10	117.9 (4)	C4—C5—H5A	119.9
C9—N—H0A	121.1	C1—C6—C5	119.5 (4)
C10—N—H0A	121.1	C1—C6—H6A	120.3
F—C1—C6	119.0 (4)	C5—C6—H6A	120.3
F—C1—C2	118.6 (4)	C8—C7—C4	131.0 (4)
C6—C1—C2	122.4 (4)	C8—C7—H7A	114.5
C1—C2—C3	118.3 (4)	C4—C7—H7A	114.5
C1—C2—H2A	120.9	C7—C8—C9	120.4 (4)
C3—C2—H2A	120.9	C7—C8—S	129.9 (3)
C2—C3—C4	121.4 (4)	C9—C8—S	109.6 (3)
C2—C3—H3A	119.3	O2—C9—N	124.0 (4)
C4—C3—H3A	119.3	O2—C9—C8	125.1 (4)
C3—C4—C5	118.2 (4)	N—C9—C8	110.9 (4)
C3—C4—C7	117.9 (4)	O1—C10—N	124.9 (4)
C5—C4—C7	123.9 (4)	O1—C10—S	126.1 (4)
C6—C5—C4	120.2 (4)	N—C10—S	109.0 (3)

F—C1—C2—C3	179.1 (5)	C4—C7—C8—S	0.6 (9)
C6—C1—C2—C3	−2.2 (9)	C10—S—C8—C7	177.2 (5)
C1—C2—C3—C4	2.1 (9)	C10—S—C8—C9	−1.5 (4)
C2—C3—C4—C5	−1.0 (8)	C10—N—C9—O2	177.5 (5)
C2—C3—C4—C7	179.8 (5)	C10—N—C9—C8	−1.9 (6)
C3—C4—C5—C6	0.0 (8)	C7—C8—C9—O2	3.9 (8)
C7—C4—C5—C6	179.1 (5)	S—C8—C9—O2	−177.2 (4)
F—C1—C6—C5	179.8 (5)	C7—C8—C9—N	−176.7 (4)
C2—C1—C6—C5	1.2 (9)	S—C8—C9—N	2.2 (5)
C4—C5—C6—C1	−0.1 (9)	C9—N—C10—O1	178.9 (6)
C3—C4—C7—C8	−174.7 (5)	C9—N—C10—S	0.7 (6)
C5—C4—C7—C8	6.3 (9)	C8—S—C10—O1	−177.6 (6)
C4—C7—C8—C9	179.3 (5)	C8—S—C10—N	0.6 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2ⁱ	0.86	1.98	2.830 (5)	171
C5—H5A···S	0.93	2.54	3.241 (5)	133
C7—H7A···O2	0.93	2.50	2.870 (5)	104

Symmetry code: (i) −x+1/2, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₀H₆FNO₂S
M_r	223.22
Crystal system, space group	Orthorhombic, Fdd2
Temperature (K)	294
a, b, c (Å)	26.519 (5), 36.509 (7), 3.8490 (8)
V (Å³)	3726.6 (13)
Z	16
Radiation type	Mo Kα
µ (mm⁻¹)	0.34
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.905, 0.967
No. of measured, independent and observed [I > 2σ(I)] reflections	2087, 1059, 790
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.121, 1.04
No. of reflections	1059
No. of parameters	136
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.66
Absolute structure	Flack (1983), no Friedel pairs
Absolute structure parameter	0.0 (2)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Siemens, 1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O2ⁱ	0.86	1.98	2.830 (5)	171.00
C5—H5A···S	0.93	2.54	3.241 (5)	133.00
C7—H7A···O2	0.93	2.50	2.870 (5)	104.00

Symmetry code: (i) −x+1/2, −y, z−1/2.

Acknowledgements

The authors thank the Center for Testing and Analysis, Nanjing University, for support.

References

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