Methyl 7-chloro-2-ethyl­sulfanyl-6-fluoro-4-oxo-4H-thio­chromene-3-carboxyl­ate

Yang Li; Tao Xiao; Dong-liang Liu; Guang-yan Yu

doi:10.1107/S1600536810002667

. 2010 Feb 27;66(Pt 3):o694. doi: 10.1107/S1600536810002667

Methyl 7-chloro-2-ethylsulfanyl-6-fluoro-4-oxo-4H-thiochromene-3-carboxylate

Yang Li ^a, Tao Xiao ^a,^*, Dong-liang Liu ^a, Guang-yan Yu ^a

PMCID: PMC2983649 PMID: 21580435

Abstract

In the title compound, C₁₃H₁₀ClFO₃S₂, the two-ring system is essentially planar, the mean plane of the benzene ring being inclined at 6.0 (2)° to the plane of the remaining four atoms. The ethylsulfanyl group is almost coplanar with the two rings [dihedral angle = 6.4 (2)°], while the carboxylate group is almost perpendicular to it [dihedral angle = 72.4 (2)°]. In the crystal structure, intermolecular C—H⋯O and C—H⋯F hydrogen bonds link the molecules in a stacked arrangement along the a axis.

Related literature

For related compounds containing a 4H-thiochromen-4-one fragment, see: Adams et al. (1991 ▶); Nakazumi et al. (1992 ▶); Weiss et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₃H₁₀ClFO₃S₂
M _r = 332.78
Triclinic,
a = 7.6740 (15) Å
b = 9.3880 (19) Å
c = 10.368 (2) Å
α = 85.18 (3)°
β = 80.93 (3)°
γ = 71.24 (3)°
V = 698.0 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.892, T _max = 0.944
2735 measured reflections
2531 independent reflections
1908 reflections with I > 2σ(I)
R _int = 0.016
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.138
S = 1.00
2531 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; 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: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810002667/zq2029sup1.cif

e-66-0o694-sup1.cif^{(17.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002667/zq2029Isup2.hkl

e-66-0o694-Isup2.hkl^{(124.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.93	2.60	3.292 (4)	132
C13—H13C⋯Fⁱⁱ	0.96	2.52	3.144 (5)	123

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

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

supplementary crystallographic information

Comment

The title compound, methyl 7-chloro-2-(ethylsulfanyl)-6-fluoro-4-oxo-4H- thiochromene-3-carboxylate (I), is a new molecule which has a potential use as antifungal. We herein report its crystal structure. The molecular structure of (I) is shown in Fig. 1, and selected geometric parameters are given in Table 1. The bond lengths and angles (Table 1) are within normal ranges (Allen et al., 1987). The molecule is essentially planar, the atoms C7, C8, C9 and S1 form a plane inclined at 6.0 (2)° with the mean plane of the phenyl ring. The ethylsulfanyl group is almost coplanar with the two rings while the carboxylate group is almost perpendicular. In the crystal structure, intermolecular C—H···O and C—H···F hydrogen bonds (Table 2) link the molecules in a stacked arrangement along the a axis (Fig. 2).

Experimental

CS₂ (1.0 g, 13.1 mmol) was dropwise added to a solution of methyl 3-(4-chloro-3-fluorophenyl)-3-oxopropanoate (4 g, 17.3 mmol) in DMSO (20 ml) containing KOH (1 g, 17.8 mmol). The yellow solution was stirred for about 2 h at room temperature. Then bromoethane (1.9 g, 17.3 mmol) was dropwise added to the intermediate. After 3 h, the solution was poured into water (50 ml). The crystalline product was isolated by filtration, washed with water (300 ml). The crystals were obtained by dissolving (I) in acetone (20 ml) and slow evaporation of the solvent at room temperature for about 7 d.