3-{2-[2-(2-Fluoro­benzyl­idene)hydrazin­yl]-1,3-thia­zol-4-yl}-2H-chromen-2-one

Afsheen Arshad; Hasnah Osman; Chan Kit Lam; Ching Kheng Quah; Hoong-Kun Fun

doi:10.1107/S1600536810018647

. 2010 May 26;66(Pt 6):o1446–o1447. doi: 10.1107/S1600536810018647

3-{2-[2-(2-Fluorobenzylidene)hydrazinyl]-1,3-thiazol-4-yl}-2H-chromen-2-one

Afsheen Arshad ^a, Hasnah Osman ^a,^‡, Chan Kit Lam ^b, Ching Kheng Quah ^c,^§, Hoong-Kun Fun ^c,^*,^¶

PMCID: PMC2979535 PMID: 21579518

Abstract

In the title compound, C₁₉H₁₂FN₃O₂S, the chromene ring system and the thiazole ring are approximately planar [maximum deviations of 0.023 (3) Å and 0.004 (2) Å, respectively]. The chromene ring system is inclined at angles of 4.78 (10) and 26.51 (10)° with respect to the thiazole and benzene rings, respectively, while the thiazole ring makes a dihedral angle of 23.07 (12)° with the benzene ring. The molecular structure is stabilized by an intramolecular C—H⋯O hydrogen bond, which generates an S(6) ring motif. The crystal packing is consolidated by intermolecular N—H⋯O hydrogen bonds, which link the molecules into chains parallel to [100], and by C—H⋯π and π–π [centroid–centroid distance = 3.4954 (15) Å] stacking interactions.

Related literature

For the synthesis of the title compound, see: Lv et al. (2010 ▶); Siddiqui et al. (2009 ▶). For general background to and the biological activity of coumarin derivatives, see: Anderson et al. (2002 ▶); Tassies et al. (2002 ▶); Mitscher (2002 ▶); Lafitte et al. (2002 ▶); Moffett (1964 ▶); Weber et al. (1998 ▶). For the biological activity of aminothiazoles derivatives, see: Hiremath et al. (1992 ▶); Habib & Khalil (1984 ▶); Karah et al. (1998 ▶); Gursoy & Karah (2000 ▶); Lednicer et al. (1990 ▶); Kim et al. (2002 ▶); Wattenberg et al. (1979 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₉H₁₂FN₃O₂S
M _r = 365.38
Orthorhombic,
a = 12.303 (2) Å
b = 10.4477 (17) Å
c = 25.247 (4) Å
V = 3245.2 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.37 × 0.08 × 0.04 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.919, T _max = 0.991
13589 measured reflections
2855 independent reflections
1971 reflections with I > 2σ(I)
R _int = 0.082

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.102
S = 1.04
2855 reflections
239 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.33 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL ; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810018647/tk2674sup1.cif

e-66-o1446-sup1.cif^{(20.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810018647/tk2674Isup2.hkl

e-66-o1446-Isup2.hkl^{(140.3KB, hkl)}

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

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

Cg1 is the centroid of the C13–C18 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9⋯O2	0.93	2.27	2.823 (3)	118
N2—H12N⋯O2ⁱ	0.85 (3)	2.04 (3)	2.852 (3)	161 (3)
C4—H4⋯Cg1ⁱⁱ	0.93	2.96	3.701 (3)	138

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

Acknowledgments

We thank the Malaysian Government and Universiti Sains Malaysia (USM) for a short-term grant (304/PKIMIA/639004) to conduct this work. HKF and CKQ thank USM for the Research University Golden Goose Grant (1001/PFIZIK/811012). CKQ also thanks USM for the award of USM Fellowship. AA thanks the Pakistan Government and PCSIR for financial support through a scholarship.

supplementary crystallographic information

Comment

Coumarin derivatives constitute an important class of heterocyclic compounds having pronounced biological activities. For example, warfarin and cenocoumarol are used as anti-coagulants (Anderson et al., 2002; Tassies et al., 2002). These compounds also possess very good anti-bacterial (Mitscher, 2002; Lafitte et al., 2002), anti-fungal (Moffett, 1964) and cytotoxic activities (Weber et al., 1998). On the other hand, aminothiazole derivatives have been reported to exhibit significant anti-fungal (Hiremath et al., 1992), anti-bacterial (Habib & Khalil, 1984), and anti-tuberculosis activities (Karah et al., 1998; Gursoy & Karah, 2000). These compounds also have very important pharmaceutical value because of their anti-inflammatory (Lednicer et al., 1990), enzyme inhibition (Kim et al., 2002) and anti-tumour activities (Wattenberg et al., 1979). Our approach is the synthesis of biologically active compounds based on the combination of different substructures to enhance the biological activity of known compounds. The title compound is a new coumarin derivative having aminothiazole moiety. We present here its crystal structure, Fig. 1.

The chromene (O1/C11–C19) ring system and thiazole (S1/N3/C8–C10) ring are approximately planar, with the maximum deviation of 0.023 (3) Å for atom C19 and 0.004 (2) Å for atom N3, respectively. The chromene ring system is inclined at angles of 4.78 (10) and 26.51 (10) ° with respect to the thiazole and benzene (C1–C6) rings, respectively. The thiazole ring makes a dihedral angle of 23.07 (12) ° with benzene ring. The molecular structure is stabilized by an intramolecular C9—H9···O2 hydrogen bond which generates an S(6) ring motif (Bernstein et al., 1995).

The crystal packing is consolidated by intermolecular N2—H12N···O2 hydrogen bonds (Fig. 2) which link the independent molecules into chains parallel to [1 0 0]. The crystal packing is consolidated by C—H···π (Table 1) and π–π stacking interactions between symmetry related S1/N3/C8—C10 (centroid Cg2) and O1/C11—C13/C18/C19 (centroid Cg3) rings, with Cg2···Cg3 distance of 3.4954 (15) Å [symmetry code: 3/2-x, -1/2+y, z].

Experimental

Thiosemicarbazide (5.00 mmol) was slowly added to a solution of 2-fluorobenzaldehyde in hot absolute ethanol (10 ml) while stirring. The resulting solution was refluxed for 2 h and then cooled on an ice bath for 45 minutes to get white precipitates. These precipitates were filtered and recrystallized from ethanol-water to obtain 2-fluorobenzaldehyde thiosemicarbazone (Lv et al., 2010). 3-[ω-Bromoacetyl coumarin] was prepared as reported in the literature (Siddiqui et al., 2009). A solution of 3-[ω-bromoacetyl coumarin] (2.50 mmol) and 2-fluorobenzaldehyde thiosemicarbazone (2.50 mmol) in chloroform-ethanol (2:1) was refluxed for 30 min. Precipitates formed were filtered and boiled in water containing sodium acetate. The product was purified by recrystallization with ethanol-chloroform (8:2).