4-Hy­droxy-3-[(4-hy­droxy-6-methyl-2-oxo-3,6-dihydro-2H-pyran-3-yl)(3-thien­yl)meth­yl]-6-methyl-3,6-dihydro-2H-pyran-2-one

Mohammad Asad; Chuan-Wei Oo; Hasnah Osman; Madhukar Hemamalini; Hoong-Kun Fun

doi:10.1107/S1600536811002716

. 2011 Jan 26;67(Pt 2):o494–o495. doi: 10.1107/S1600536811002716

4-Hydroxy-3-[(4-hydroxy-6-methyl-2-oxo-3,6-dihydro-2H-pyran-3-yl)(3-thienyl)methyl]-6-methyl-3,6-dihydro-2H-pyran-2-one

Mohammad Asad ^a, Chuan-Wei Oo ^a,^‡, Hasnah Osman ^a, Madhukar Hemamalini ^b, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC3051638 PMID: 21523150

Abstract

The asymmetric unit of the title compound, C₁₇H₁₄O₆S, contains four crystallographically independent molecules in which the pyranone units are essentially planar, with maximum deviations of 0.016 (2), 0.019 (2), 0.025 (2), 0.014 (2), 0.020 (2), 0.010 (2), 0.003 (2) and 0.012 (2) Å. One of the thiophene rings is disordered over two positions, with an occupancy ratio of 0.739 (4):0.261 (4). The dihedral angles between the two pyranone rings in the independent molecules are 59.42 (8), 48.67 (8), 60.62 (9) and 51.60 (8)°. In the crystal, molecules are linked through intermolecular O—H⋯O and C—H⋯O hydrogen bonds, forming a three-dimensional network.

Related literature

For general background to the synthesis and activities of polyketide compounds, see: Bentley (1999 ▶); Eckermann et al. (2003 ▶); Abe et al. (2005 ▶); Fang et al. (2010 ▶); Lee et al. (2000 ▶); Shyamsunder & Hermann (1999 ▶). For bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₇H₁₄O₆S
M _r = 346.34
Orthorhombic,
a = 30.6120 (18) Å
b = 7.9982 (5) Å
c = 25.6540 (15) Å
V = 6281.1 (7) Å³
Z = 16
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100 K
0.45 × 0.40 × 0.18 mm

Data collection

Bruker APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.902, T _max = 0.958
127650 measured reflections
19406 independent reflections
18459 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.131
S = 1.07
19406 reflections
896 parameters
77 restraints
H-atom parameters constrained
Δρ_max = 0.98 e Å⁻³
Δρ_min = −0.75 e Å⁻³
Absolute structure: Flack (1983 ▶), 9485 Friedel pairs
Flack parameter: 0.03 (4)

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/S1600536811002716/rz2545sup1.cif

e-67-0o494-sup1.cif^{(51KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811002716/rz2545Isup2.hkl

e-67-0o494-Isup2.hkl^{(929.3KB, 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
O2A—H2OA⋯O6A	0.82	1.78	2.562 (2)	159
O5A—H5OA⋯O6D	0.82	1.84	2.634 (2)	164
O2B—H2OB⋯O6Cⁱ	0.82	1.85	2.631 (2)	158
O5B—H5OB⋯O3B	0.82	1.71	2.529 (2)	171
O2C—H2OC⋯O6Bⁱⁱ	0.82	1.84	2.663 (2)	175
O5C—H5OC⋯O3C	0.82	1.76	2.549 (2)	163
O2D—H2OD⋯O3A	0.82	1.82	2.6205 (19)	166
O5D—H5OD⋯O3D	0.82	1.81	2.546 (2)	148
C3A—H3AA⋯O3C	0.93	2.45	3.306 (3)	154
C8A—H8AA⋯O6D	0.93	2.38	3.072 (2)	131
C3B—H3BA⋯O6Aⁱⁱⁱ	0.93	2.51	3.258 (2)	138
C3C—H3CA⋯O6Bⁱⁱ	0.93	2.52	3.193 (3)	130
C11A—H11A⋯O3A	0.98	2.34	2.871 (2)	113
C11A—H11A⋯O5A	0.98	2.30	2.805 (2)	111
C11B—H11B⋯O2B	0.98	2.22	2.768 (2)	114
C11B—H11B⋯O6B	0.98	2.27	2.835 (2)	115
C11C—H11C⋯O2C	0.98	2.35	2.826 (2)	109
C11C—H11C⋯O6C	0.98	2.36	2.875 (2)	112
C11D—H11D⋯O2D	0.98	2.23	2.777 (2)	114
C11D—H11D⋯O6D	0.98	2.27	2.833 (2)	115
C13A—H13A⋯O4C^iv	0.93	2.39	3.278 (8)	159
C13B—H13C⋯O1A^v	0.93	2.51	3.311 (3)	145
C13D—H13E⋯O1B^vi	0.93	2.59	3.366 (2)	142
C14A—H14A⋯O3C^vii	0.93	2.33	3.183 (4)	152
C14C—H14D⋯O1C^vii	0.93	2.52	3.377 (2)	154
C16B—H16D⋯O6Aⁱⁱⁱ	0.96	2.58	3.382 (3)	141

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) .

Acknowledgments

MA, CWO and HO thank Universiti Sains Malaysia (USM) for providing necessary research facilities and RU research funding under grant No. 1001/PKIMIA/811134. MA also thanks USM for the award of a post-doctoral fellowship. HKF and MH thank the Malaysian Government and USM for the Research University grant No. 1001/PFIZIK/811160. MH also thanks USM for a post-doctoral research fellowship.

supplementary crystallographic information

Comment

4-Hydroxy-6-methyl-2-pyrone (triacetic acid lactone) is a polyketide (Bentley, 1999) for polyketomethylene compounds CH₃(-CO–CH₂-)_n and is absorbed in the biosynthesis of natural products. In recent years, triacetic acid lactone has been found to be the precursor of a phytoalexin in plant Gerbara hybrid (Eckermann et al., 2003; Abe et al., 2005). Polyketides exist as diverse groups in many natural products exhibiting significant physiological effects and their derivatives have been used as anticancer (Fang et al., 2010), anti-HIV (Lee et al., 2000), convulsants and antiepileptics agents (Shyamsunder & Hermann, 1999).

The asymmetric unit of the title compound, consists of four crystallographically independent molecules, (A, B, C & D), as shown in Fig. 1. The bond lengths and angles of molecules A, B, C and D agree with each other and are within normal ranges (Allen et al., 1987). Each molecule consists of two pyranone rings and one thiophene ring. The pyranone units are essentially planar with maximum deviations of 0.016 (2) Å for atom C2A: 0.019 (2) Å for atom C9A (molecule A), 0.025 (2) Å for atom C5B: 0.014 (2) Å for atom C10B (molecule B), 0.020 (2) Å for atom O1C: 0.010 (2) Å for atom C7C (molecule C) and 0.003 (2) Å for atom C10D : 0.012 (2) Å for atom C5D (molecule D). In molecule A, the thiophene ring is disordered over two positions, with occupancy ratio of 0.739 (4):0.261 (4). The dihedral angle between the two pyranone (O1/C1–C5)/(O4/C6–C10) rings are: 59.42 (8)° in molecule A, 48.67 (8)° in molecule B, 60.62 (9)° in molecule C and 51.60 (8)° in molecule D.

In the crystal structure (Fig. 2), the molecules are linked through intermolecular O—H···O and C—H···O hydrogen bonds (Table 1) to form a three-dimensional network.

Experimental

A mixture of thiophene-3-carboxaldehyde (4.46 mmol, 0.5 g) and 4-hydroxy-6-methylpyrone (8.92 mmol, 1.12 g) in 20 ml of methanol was stirred at room temperature for overnight. The completion of the reaction was monitored by TLC. After the reaction was completed, the crude product that separated, filtered, washed with methanol and dried. The isolated product was further purified by recrystallization from chloroform-methanol (1:1 v/v) to give the pure title compound in 67% yield.