4-Methyl-2-oxo-2H-chromen-7-yl 4-meth­oxy­benzene­sulfonate

Suman Sinha; Hasnah Osman; Habibah A Wahab; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536811049476

. 2011 Nov 30;67(Pt 12):o3457. doi: 10.1107/S1600536811049476

4-Methyl-2-oxo-2H-chromen-7-yl 4-methoxybenzenesulfonate

Suman Sinha ^a, Hasnah Osman ^b, Habibah A Wahab ^a,^‡, Madhukar Hemamalini ^c, Hoong-Kun Fun ^c,^*,^§

PMCID: PMC3239087 PMID: 22199935

Abstract

In the title compound, C₁₇H₁₄O₆S, the 2H-chromene ring is essentially planar, with a maximum deviation of 0.016 (1) Å. The dihedral angle between the 2H-chromene and the benzene rings is 54.61 (5)°. The C atom of the methoxy group is close to coplanar with its attached ring [deviation = 0.082 (2) Å]. In the crystal, molecules are connected via C—H⋯O hydrogen bonds, forming sheets lying parallel to the bc plane. Weak C—H⋯π interactions are also observed.

Related literature

For applications and properties of coumarin derivatives, see: Sinha et al. (2011 ▶); Valente et al. (2010) ▶; Radanyi et al. (2008 ▶); Han et al. (2005 ▶); Cheng et al. (2004 ▶). For further synthetic details, see: Fusegi et al. (2009 ▶).

Experimental

Crystal data

C₁₇H₁₄O₆S
M _r = 346.34
Triclinic,
a = 7.9801 (3) Å
b = 9.2234 (4) Å
c = 10.9682 (5) Å
α = 99.049 (1)°
β = 90.288 (1)°
γ = 93.945 (1)°
V = 795.26 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 K
0.39 × 0.34 × 0.17 mm

Data collection

Bruker APEXII DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.913, T _max = 0.962
21468 measured reflections
5907 independent reflections
4468 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.131
S = 1.04
5907 reflections
219 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.36 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 datablock(s) global, I. DOI: 10.1107/S1600536811049476/hb6524sup1.cif

e-67-o3457-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811049476/hb6524Isup2.hkl

e-67-o3457-Isup2.hkl^{(283.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811049476/hb6524Isup3.cml

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

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

Cg1 is the centroid of the O2/C9–C13 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8A⋯O3ⁱ	0.93	2.50	3.4156 (16)	169
C15—H15A⋯O5ⁱⁱ	0.93	2.44	3.2923 (17)	153
C16—H16B⋯Cg1ⁱⁱⁱ	0.96	2.96	3.8423 (17)	154

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

Acknowledgments

HAW gratefully acknowledges the Malaysian Ministry of Science, Technology and Innovation for the synthesis work funded by grants Nos. 09-05-lfn-meb-004 and 304/PFARMASI/650545/I-121. HKF and MH thank the Malaysian Government and Universiti Sains Malaysia for the Research University Grant No. 1001/PFIZIK/811160. MH thanks also Universiti Sains Malaysia for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

This is the continuation of our work regarding synthesis of derivatives of sulphur-containing small molecules (Sinha et al., 2011). Coumarin derivatives have been tested successfully against Cdc25 phosphatases (Valente et al., 2010), HSP 90 (Radanyi et al., 2008), MEK1 (Han et al., 2005) as well as TNF-α (Cheng et al., 2004). Apart from these biological activity, this class of molecules is also widely used as fluorescent labels for molecular studies of nucleic acids and proteins.

The asymmetric unit of the title compound is shown in Fig. 1. The 2H-chromene (O2/C7–C15) ring is essentially planar, with a maximum deviation of 0.016 (1) Å for atom O2. The dihedral angle between the 2H-chromene (O2/C7–C15) ring and benzene (C1–C6) ring is 54.61 (5)°.

In the crystal, (Fig. 2), the molecules are connected via weak intermolecular C—H···O hydrogen bonds (Table 1) to form two-dimensional networks parallel to the bc-plane. Furthermore, the crystal structure is stabilized by weak C—H···π interactions involving the Cg1 (O2/C9–C13) ring.

Experimental

The synthetic procedure followed is modified from the recent work by Fusegi et al. (2009). A mixture of 4-methylumbelliferone (0.176 g, 1.00 mmol), K₂CO₃ (0.345 g, 2.5 mmol), and 4 Methoxybenzene sulphonyl chloride (0.130 g, 1.1 mmol) in ethyl acetate (10 ml) was refluxed for 5 hrs. After cooling, the solvent was evaporated under reduced pressure. H₂O (30 ml) was added to the residue and the contents was extracted with AcOEt (3 × 100 ml). The combined organic layer was washed with H₂O (3 × 80 ml) and brine (1 × 100 ml) and was dried over MgSO₄. The solvent was evaporated in vacuo and the residue was recrystallized from hexane - AcOEt (7: 1) to give the title compound as colourless blocks.