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

In the title compound, C₁₀H₆FNO₂S, the benzene and thia­zolidine rings are oriented at a dihedral angle of 8.90 (3)°. Intra­molecular C—H...O, C—H...F and C—H...S hydrogen bonds result in the formation of two nearly planar five-membered rings and one non-planar six-membered ring, the five-membered rings being also nearly coplanar with the adjacent rings. In the crystal structure, inter­molecular N—H...O and C—H...O hydrogen bonds link the mol­ecules.

Key indicators

• Single-crystal X-ray study
• T = 294 K
• Mean [sigma](C-C) = 0.007 Å
• R factor = 0.060
• wR factor = 0.173
• Data-to-parameter ratio = 13.6

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ...          7
PLAT432_ALERT_2_C Short Inter X...Y Contact  C9     ..  C9      ..       3.15 Ang.
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          1

Alert level G
PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints .......         48

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   3 ALERT level C = Check and explain
   1 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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 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), the bond lengths and angles are within normal ranges (Allen et al., 1987). The intramolecular C—H···O, C—H···F and C—H···S hydrogen bonds (Table 1) result in the formation of the nearly planar five-membered rings; C (F/C3/C4/C7/H7A) and D (O1/C7–C9/H7A), and one non-planar six-membered ring E (S/C4/C5/C7/C8/H5A), the five-membered rings being also nearly co-planar with the adjacent rings A (C1–C6) and B (S/N/C8–C10). The dihedral angles between them are A/C = 2.08 (2)° and B/D = 1.18 (3)°. The planar rings A (C1–C6) and B (S/N/C8–C10) are oriented at a dihedral angle of 8.90 (3)°.

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

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).

S2. Experimental

Thiazolidine-2,4-dione (10 mmol) and 2-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, the crude compound filtered out, and recrystallized from ethanol. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.

S3. Refinement

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C,N).

Computing details

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, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL (Siemens, 1996).

Figures

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

Crystal data

C10H6FNO2S	F(000) = 456
Mr = 223.22	Dx = 1.570 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 5.120 (1) Å	θ = 9–13°
b = 21.189 (4) Å	µ = 0.33 mm^−1
c = 9.0310 (18) Å	T = 294 K
β = 105.49 (3)°	Block, colourless
V = 944.2 (3) Å^3	0.40 × 0.10 × 0.10 mm
Z = 4

Data collection

Enraf–Nonius CAD-4 diffractometer	1283 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 25.9°, θmin = 1.9°
ω/2θ scans	h = −6→6
Absorption correction: ψ scan (North et al., 1968)	k = 0→26
Tmin = 0.878, Tmax = 0.967	l = 0→11
2060 measured reflections	3 standard reflections every 120 min
1853 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.173	H-atom parameters constrained
S = 1.00	w = 1/[σ^2(Fo^2) + (0.05P)^2 + 3P] where P = (Fo^2 + 2Fc^2)/3
1853 reflections	(Δ/σ)max < 0.001
136 parameters	Δρmax = 0.38 e Å^−3
48 restraints	Δρmin = −0.47 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
S	0.4369 (2)	0.65416 (5)	0.48345 (13)	0.0472 (3)
N	0.7813 (7)	0.57028 (17)	0.4442 (4)	0.0435 (9)
H0A	0.8957	0.5506	0.4065	0.052*
F	0.2877 (8)	0.53827 (18)	0.9920 (4)	0.0975 (13)
O1	0.8214 (7)	0.50293 (14)	0.6463 (4)	0.0489 (8)
C1	−0.0740 (10)	0.6837 (3)	0.9594 (6)	0.0605 (13)
H1A	−0.1900	0.7048	1.0060	0.073*
O2	0.6738 (7)	0.64701 (16)	0.2582 (4)	0.0585 (9)
C2	0.0270 (10)	0.6253 (3)	1.0131 (5)	0.0589 (13)
H2A	−0.0176	0.6068	1.0965	0.071*
C3	0.1953 (10)	0.5952 (2)	0.9402 (5)	0.0527 (12)
C4	0.2695 (8)	0.6197 (2)	0.8152 (5)	0.0389 (9)
C5	0.1655 (10)	0.6795 (2)	0.7646 (5)	0.0520 (11)
H5A	0.2109	0.6984	0.6819	0.062*
C6	−0.0040 (11)	0.7108 (2)	0.8368 (6)	0.0591 (13)
H6A	−0.0711	0.7504	0.8021	0.071*
C7	0.4484 (8)	0.5833 (2)	0.7487 (5)	0.0408 (10)
H7A	0.5179	0.5470	0.8029	0.049*
C8	0.5305 (8)	0.5934 (2)	0.6216 (5)	0.0400 (9)
C9	0.7224 (8)	0.55010 (19)	0.5755 (5)	0.0374 (9)
C10	0.6489 (9)	0.6235 (2)	0.3753 (5)	0.0462 (10)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S	0.0537 (7)	0.0454 (6)	0.0477 (6)	0.0082 (5)	0.0226 (5)	0.0061 (5)
N	0.048 (2)	0.046 (2)	0.046 (2)	0.0069 (16)	0.0288 (17)	0.0035 (16)
F	0.124 (3)	0.101 (3)	0.094 (3)	0.053 (2)	0.075 (2)	0.051 (2)
O1	0.061 (2)	0.0406 (16)	0.0552 (19)	0.0089 (14)	0.0323 (16)	0.0024 (14)
C1	0.054 (3)	0.074 (3)	0.057 (3)	0.011 (2)	0.022 (2)	−0.020 (2)
O2	0.073 (2)	0.062 (2)	0.0510 (19)	0.0049 (18)	0.0348 (17)	0.0121 (16)
C2	0.055 (3)	0.085 (3)	0.045 (2)	0.008 (3)	0.027 (2)	−0.003 (2)
C3	0.062 (3)	0.063 (3)	0.041 (2)	0.012 (2)	0.027 (2)	0.007 (2)
C4	0.037 (2)	0.047 (2)	0.037 (2)	0.0007 (18)	0.0169 (17)	−0.0062 (17)
C5	0.064 (3)	0.047 (2)	0.052 (3)	0.009 (2)	0.027 (2)	0.000 (2)
C6	0.070 (3)	0.049 (3)	0.066 (3)	0.008 (2)	0.031 (3)	−0.010 (2)
C7	0.044 (2)	0.039 (2)	0.042 (2)	0.0083 (18)	0.0166 (19)	0.0022 (18)
C8	0.042 (2)	0.042 (2)	0.040 (2)	−0.0025 (18)	0.0171 (18)	−0.0029 (18)
C9	0.039 (2)	0.038 (2)	0.040 (2)	−0.0034 (18)	0.0188 (18)	−0.0008 (18)
C10	0.044 (2)	0.054 (3)	0.042 (2)	−0.001 (2)	0.0143 (19)	0.000 (2)

Geometric parameters (Å, º)

S—C10	1.767 (5)	C2—C3	1.374 (6)
S—C8	1.767 (4)	C2—H2A	0.9300
N—C9	1.368 (5)	C3—C4	1.385 (6)
N—C10	1.376 (6)	C4—C5	1.403 (6)
N—H0A	0.8600	C4—C7	1.444 (5)
F—C3	1.333 (6)	C5—C6	1.385 (6)
O1—C9	1.221 (5)	C5—H5A	0.9300
C1—C6	1.377 (7)	C6—H6A	0.9300
C1—C2	1.378 (7)	C7—C8	1.341 (6)
C1—H1A	0.9300	C7—H7A	0.9300
O2—C10	1.206 (5)	C8—C9	1.483 (6)
C10—S—C8	91.8 (2)	C6—C5—H5A	119.7
C9—N—C10	116.9 (3)	C4—C5—H5A	119.7
C9—N—H0A	121.6	C1—C6—C5	120.6 (5)
C10—N—H0A	121.6	C1—C6—H6A	119.7
C6—C1—C2	120.2 (4)	C5—C6—H6A	119.7
C6—C1—H1A	119.9	C8—C7—C4	130.5 (4)
C2—C1—H1A	119.9	C8—C7—H7A	114.8
C3—C2—C1	118.2 (5)	C4—C7—H7A	114.8
C3—C2—H2A	120.9	C7—C8—C9	121.6 (4)
C1—C2—H2A	120.9	C7—C8—S	129.2 (3)
F—C3—C2	117.5 (4)	C9—C8—S	109.2 (3)
F—C3—C4	118.4 (4)	O1—C9—N	123.6 (4)
C2—C3—C4	124.0 (5)	O1—C9—C8	125.0 (4)
C3—C4—C5	116.2 (4)	N—C9—C8	111.4 (4)
C3—C4—C7	118.7 (4)	O2—C10—N	125.5 (4)
C5—C4—C7	125.1 (4)	O2—C10—S	123.9 (4)
C6—C5—C4	120.7 (4)	N—C10—S	110.6 (3)
C6—C1—C2—C3	−0.7 (8)	C4—C7—C8—S	−2.9 (8)
C1—C2—C3—F	−178.9 (5)	C10—S—C8—C7	−179.8 (4)
C1—C2—C3—C4	−0.3 (8)	C10—S—C8—C9	−1.2 (3)
F—C3—C4—C5	179.6 (5)	C10—N—C9—O1	178.5 (4)
C2—C3—C4—C5	1.0 (7)	C10—N—C9—C8	−2.9 (5)
F—C3—C4—C7	−1.5 (7)	C7—C8—C9—O1	−0.3 (7)
C2—C3—C4—C7	179.9 (5)	S—C8—C9—O1	−179.0 (4)
C3—C4—C5—C6	−0.8 (7)	C7—C8—C9—N	−178.8 (4)
C7—C4—C5—C6	−179.6 (4)	S—C8—C9—N	2.4 (4)
C2—C1—C6—C5	0.9 (8)	C9—N—C10—O2	−178.8 (4)
C4—C5—C6—C1	−0.1 (8)	C9—N—C10—S	1.9 (5)
C3—C4—C7—C8	173.4 (5)	C8—S—C10—O2	−179.6 (4)
C5—C4—C7—C8	−7.8 (8)	C8—S—C10—N	−0.3 (3)
C4—C7—C8—C9	178.7 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0A···O1^i	0.86	2.00	2.846 (5)	170
C2—H2A···O2^ii	0.93	2.57	3.243 (6)	130
C5—H5A···S	0.93	2.56	3.248 (5)	131
C6—H6A···O2^iii	0.93	2.51	3.417 (6)	165
C7—H7A···F	0.93	2.33	2.717 (6)	105
C7—H7A···O1	0.93	2.54	2.889 (6)	102

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, y, z+1; (iii) x−1, −y+3/2, z+1/2.