4-Hy­droxy-3-[(4-hy­droxy-2-oxo-2H-3-chromen­yl)(3-thien­yl)meth­yl]-2H-chromen-2-one

Mohammad Asad; Chuan-Wei Oo; Hasnah Osman; Mohd Mustaqim Rosli; Hoong-Kun Fun

doi:10.1107/S1600536811011676

. 2011 Apr 7;67(Pt 5):o1037–o1038. doi: 10.1107/S1600536811011676

4-Hydroxy-3-[(4-hydroxy-2-oxo-2H-3-chromenyl)(3-thienyl)methyl]-2H-chromen-2-one

Mohammad Asad ^a, Chuan-Wei Oo ^a,^‡, Hasnah Osman ^a, Mohd Mustaqim Rosli ^b, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC3089123 PMID: 21754365

Abstract

The whole molecule of the title compound, C₂₃H₁₄O₆S, is disordered over two sets of sites with refined occupancies of 0.8733 (12):0.1267 (12). The dihedral angle between the mean planes through the chromene ring systems is 56.31 (5) and 55.2 (3)° for the major and minor components, respectively. In both components, a pair of intramolecular O—H⋯O interactions generate rings of S(8) graph-set motif. In the crystal, the molecules are linked by intermolecular C—H⋯O interactions, forming chains along the b axis. The structure is further stabilized by π–π interactions with centroid–centroid distances of 3.594 (2) and 3.608 (5) Å.

Related literature

For the biological activity of 4-hydroxycoumarins, see: Abdelhafez et al. (2010 ▶); Huang et al. (2010 ▶); Jacquot et al. (2001 ▶); Kokil et al. (2010 ▶); Siddiqui & Asad (2010 ▶); Skulnick et al. (1997 ▶); Sullivan et al. (1943 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₃H₁₄O₆S
M _r = 418.40
Monoclinic,
a = 7.8225 (2) Å
b = 8.9426 (2) Å
c = 27.1317 (6) Å
β = 100.679 (1)°
V = 1865.09 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 297 K
0.49 × 0.44 × 0.16 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.902, T _max = 0.966
20839 measured reflections
5420 independent reflections
3497 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.106
S = 1.02
5420 reflections
524 parameters
252 restraints
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.21 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/S1600536811011676/rz2575sup1.cif

e-67-o1037-sup1.cif^{(34.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011676/rz2575Isup2.hkl

e-67-o1037-Isup2.hkl^{(265.4KB, 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
O3—H3B⋯O4	0.82	1.89	2.7049 (19)	180
O6—H6B⋯O5	0.82	1.79	2.612 (2)	179
C21—H21A⋯O4ⁱ	0.93	2.56	3.475 (8)	168
O3X—H3XB⋯O4X	0.82	1.86	2.682 (15)	178
O6X—H6XB⋯O5X	0.82	1.69	2.49 (2)	168
C23X—H23B⋯O3Xⁱ	0.93	2.53	3.31 (5)	142

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are thankful to Universiti Sains Malaysia (USM) for providing the necessary research facilities and RU research funding under the grant No. 1001/PKIMIA/811134. MA also thanks Universiti Sains Malaysia for the award of post-doctoral fellowship. HKF and MMR thank USM for the Research University Grant (No. 1001/PFIZIK/811160).

supplementary crystallographic information

Comment

The colourless crystalline bis 4-hydroxycoumarins are obtained from the condensation of coumarin and aldehyde derivatives (Sullivan et al., 1943). A large number of structurally novel 4-hydroxycoumarin derivatives have exhibited estrogenic activity on MCF-7 breast carcinoma cells (Jacquot et al., 2001) and possess several types of biological activities such as antifungal (Kokil et al., 2010), anticoagulant (Abdelhafez et al., 2010) anticancer (Huang et al., 2010), anti-HIV (Skulnick et al., 1997), antibacterial and anti-inflammatory (Siddiqui & Asad, 2010) activities.

In the title compound (Fig. 1), the whole molecule is disordered over two orientations with refined site occupancies of 0.873 (1):0.127 (1). The chromene ring systems are almost planar, with maximum deviation of 0.099 (3) Å for atom C9A (major component, Fig. 2) and 0.12 (2) Å for atom C11X (minor component, Fig. 3). The dihedral angles they form are 56.31 (5) and 55.2 (3)° for the major and minor components, respectively. Two pairs of intramolecular hydrogen bonds, O3—H3B···O4, O6—H6B···O5 (major component) and O3X—H3XB···O4X, O6X—H6XB···O5X (minor component), generate rings of S(8) graph-set motifs (Table 1; Bernstein et al., 1995). In the crystal packing, intermolecular C—H···O hydrogen interactions (Table 1) link the molecules into chains along the b axis (Fig. 4). π—π stacking interactions with centroid-to-centroid distances of 3.594 (2) (major component) and 3.608 (5) Å (minor component) are also observed.

Experimental

To a well-stirred solution of 4-hydroxycoumarin (6.17 mmol, 1.0 g) in ethanol (10 ml) containing two drops of acetic acid, thiophene-3-carboxaldehyde (3.1 mmol, 0.345 g) was added. The reaction mixture was stirred at room temperature for 8 hr. The completion of the reaction was monitored by TLC. After the reaction was completed, the crystallized solid was separated out, filtered, washed with ethanol and dried. The isolated product was further purified by recrystallization from a chloroform / methanol mixture (1:1 v/v) to give the pure title compound in 70% yield.