8-Formyl-4-methyl-2-oxo-2H-chromen-7-yl 4-methyl­benzenesulfonate

H Yuvaraj; D Gayathri; Rajesh G Kalkhambkar; Geeta M Kulkarni; Rajendra M Bapset

doi:10.1107/S1600536811018927

. 2011 May 25;67(Pt 6):o1513. doi: 10.1107/S1600536811018927

8-Formyl-4-methyl-2-oxo-2H-chromen-7-yl 4-methylbenzenesulfonate

H Yuvaraj ^a,^*, D Gayathri ^b, Rajesh G Kalkhambkar ^c, Geeta M Kulkarni ^c, Rajendra M Bapset ^d

PMCID: PMC3120547 PMID: 21754878

Abstract

In the title compound, C₁₈H₁₄O₆S, the coumarin ring system is nearly planar, with a maximum out-of-plane deviation of 0.032 (2) Å. The dihedral angle between the benzene ring and the coumarin ring system is 32.41 (8)°. The crystal packing is stabilized by intermolecular C—H⋯O interactions, generating C(8), C(10) and C(11) chains and an R ₂ ²(10) ring. The formyl group is disordered over two sets of sites, with occupancies of 0.548 (5) and 0.452 (5).

Related literature

For the biological activity of coumarins, see: Carlton et al. (1996 ▶); El-Agrody et al. (2001 ▶); Emmanuel-Giota et al. (2001 ▶); Kulkarni et al. (2006 ▶); Kalkhambkar et al. (2008 ▶); Shaker (1996 ▶); Yang et al. (2005 ▶); Zhou et al. (2000 ▶). For a related structure, see: Yuvaraj et al. (2011 ▶).

Experimental

Crystal data

C₁₈H₁₄O₆S
M _r = 358.35
Orthorhombic,
a = 17.6174 (7) Å
b = 7.2025 (3) Å
c = 25.7706 (10) Å
V = 3270.0 (2) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 K
0.14 × 0.13 × 0.13 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
48911 measured reflections
4234 independent reflections
3095 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.135
S = 1.02
4234 reflections
238 parameters
14 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; 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: WinGX (Farrugia, 1999 ▶) and PARST (Nardelli, 1995 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811018927/is2704sup1.cif

e-67-o1513-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811018927/is2704Isup2.hkl

e-67-o1513-Isup2.hkl^{(203.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811018927/is2704Isup3.cml

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
C4—H4⋯O6ⁱ	0.93	2.56	3.326 (2)	140
C13—H13⋯O6ⁱⁱ	0.93	2.52	3.343 (2)	148
C16—H16⋯O2ⁱⁱⁱ	0.93	2.51	3.433 (2)	175

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

Acknowledgments

HY acknowledges Yeungnam University for the opportunity to work as a Full-Time Foreign Instructor.

supplementary crystallographic information

Comment

Coumarins are the class of lactones with extensive occurrence in plants possessing wide range of biological activities (Kulkarni et al., 2006). Many synthetic and naturally occurring coumarins are well documented for their wide range of biological activities such as antibacterial (El-Agrody et al., 2001), antifungal (Shaker, 1996), antioxidant (Yang et al., 2005), analgesic (Kalkhambkar et al., 2008) and anti-inflammatory (Emmanuel-Giota et al., 2001) properties. A large number of natural and semisynthetic coumarin and bicoumarin derivatives have been reported to demonstrate chemopreventive (Carlton et al., 1996) and anti-HIV (Zhou et al., 2000) activities. In view of various biological properties associated with coumarins, we have synthesized the title compound and report here its structure.

The molecular structure of the title compound is shown in Fig.1. Bond lengths and bond angles are comparable with the similar structure (Yuvaraj et al., 2011). Positional disorder has been observed for formyl oxygen atom with C14—O4A and C14—O4B bond lengths being 1.137 (3) and 1.109 (4) Å, respectively. The coumarin ring system is nearly planar with a maximum out-of-plane deviation of 0.032 (2) Å (r.m.s. deviation = 0.021 Å). Dihedral angle between the C2–C7 benzene ring and the C8–C13 benzene ring of the coumarin moeity is 33.3 (1)°. Atoms O6 and C18 lie -0.017 (3) and 0.073 (3) Å, respectively, from the least-squares plane of the atoms (C10/C11/C17/C16/C15/O5, r.m.s. deviation = 0.012 Å). Atom C1 lies 0.030 (4) Å from the least-squares plane of the phenyl ring (r.m.s. deviation = 0.007 Å).

The crystal packing is stabilized by C—H···O intermolecular interactions. C4—H4···O6ⁱ interaction generates a helical C(11) chain along the [010] direction. Interactions C13—H13···O6ⁱⁱ and C16—H16···O2ⁱⁱⁱ generate C(8) and C(10) chains, respectively, running along [100]. In addition, the interactions C13—H13···O6ⁱⁱ and C16—H16···O2ⁱⁱⁱ generate an R₂²(10) ring.

Experimental

A mixture of 8-formyl-7-hydroxy-4-methyl coumarin (6 mmol), p-toluenesulfonylchloride (6 mmol) and powdered anhydrous K₂CO₃ (6 mmol) in 20 ml of super dry acetone was stirred in room temperature for 12 h. After the completion of the reaction, the solvent was removed under reduced pressure and separated the solids by filtration. It was then washed with 50 ml of dilute hydrochloric acid, excess of cold water, dried and crystallized from ethanol and dioxan mixture. Yield 80%; Light green crystalline solid (ethanol + dioxan); m.p. 180–182 °C; R_f 0.43 (benzene); IR (KBr) cm^-1 1734, 1708, 1303; ¹H NMR (CDCl₃) δ 2.47 (3H, s), 2.51 (3H, s), 6.35 (1H, s), 7.32 (6H, m), 10.34 (1H, s); Anal. Calcd. for C₁₈H₁₄O₆S: C 60.33, H 3.94; Found: C 60.13, H 3.70.