3-Hy­droxy-2-(4-meth­oxy­phen­yl)-4H-chromen-4-one

Michał Wera; Ilia E Serdiuk; Alexander D Roshal; Jerzy Błażejowski

doi:10.1107/S160053681100167X

. 2011 Jan 22;67(Pt 2):o440. doi: 10.1107/S160053681100167X

3-Hydroxy-2-(4-methoxyphenyl)-4H-chromen-4-one

Michał Wera ^a, Ilia E Serdiuk ^b, Alexander D Roshal ^b, Jerzy Błażejowski ^a,^*

PMCID: PMC3051573 PMID: 21523104

Abstract

In the title compound, C₁₆H₁₂O₄, the benzene ring is twisted at an angle of 12.3 (1)° relative to the 4H-chromene skeleton, and an intramolecular O—H⋯O hydrogen bond occurs. The methoxy group is almost coplanar with the benzene ring [1.5 (1)°]. In the crystal, inversely oriented molecules are arranged in double (A, A′) columns, along the b axis, and are linked by a network of intermolecular O—H⋯O hydrogen bonds (between A and A′) and C—H⋯π contacts (within A or A′). The 4H-chromene cores are parallel within A or A′, but make a dihedral angle of 88.6 (1)° between A and A′.

Related literature

For general features of flavonols (derivatives of 3-hydroxy-2-phenyl-4H-chromen-4-one), see: Demchenko (2009 ▶); Klymchenko et al. (2003 ▶); Sengupta & Kasha (1979 ▶). For related structures, see: Etter et al. (1986 ▶); Waller et al. (2003 ▶); Wera et al. (2011 ▶). For intermolecular interactions, see: Aakeröy et al. (1992 ▶); Takahashi et al. (2001 ▶). For the synthesis, see: Sobottka et al. (2000 ▶).

Experimental

Crystal data

C₁₆H₁₂O₄
M _r = 268.26
Monoclinic,
a = 11.2400 (5) Å
b = 4.9860 (2) Å
c = 21.9907 (9) Å
β = 95.116 (4)°
V = 1227.51 (9) Å³
Z = 4
Cu Kα radiation
μ = 0.87 mm⁻¹
T = 295 K
0.4 × 0.05 × 0.05 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.723, T _max = 0.888
7763 measured reflections
2209 independent reflections
1691 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.112
S = 1.04
2209 reflections
185 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681100167X/om2398sup1.cif

e-67-0o440-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100167X/om2398Isup2.hkl

e-67-0o440-Isup2.hkl^{(108.6KB, hkl)}

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

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

Cg1 is the centroid of the C13–C18 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O11—H11⋯O12	0.91 (3)	2.17 (3)	2.672 (2)	114 (2)
O11—H11⋯O12ⁱ	0.91 (3)	1.92 (3)	2.748 (2)	149 (2)
C20—H20B⋯Cg1ⁱⁱ	0.96	2.87	3.710 (2)	147

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

Acknowledgments

This study was financed by the State Funds for Scientific Research (grant DS/8220–4–0087–11).

supplementary crystallographic information

Comment

3-Hydroxy-2-phenyl-4H-chromen-4-one (flavonol) and its derivatives exhibit dual fluorescence in liquids arising from Excited State Intramolecular Proton Transfer (ESIPT) (Sengupta & Kasha, 1979). Both ESIPT and the fluorescence of flavonols depend substantially on the structure of the compounds (the angle between 4H-chromene and benzene moieties (Klymchenko et al., 2003)) and the properties of the medium, which makes them convenient analytical probes in chemistry, biochemistry, biology and medicine (Demchenko, 2009). Here we present the crystal structure of a flavonol derivative – 3-hydroxy-2-(4-methoxyphenyl)-4H-chromen-4-one – a potential fluorescence sensor.

In the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the 4H-chromen-4-one moiety are similar to those in 2-phenyl-4H-chromen-4-one (flavone) (Waller et al., 2003) and 3-hydroxy-2-phenyl-4H-chromen-4-one (flavonol) (Etter et al., 1986). With respective average deviations from planarity of 0.0070 (2)° and 0.0055 (2)°, the 4H-chromene and benzene ring systems are oriented at a dihedral angle of 12.3 (1)° (in the case of flavonol this angle is equal to 5.5 (1)° (Etter et al., 1986), while 3-hydroxy-2-(4-hydroxyphenyl)-4H-chromen-4-one – 20.7 (1)° (Wera et al., 2011)). The methoxy group remains almost in the plane of the benzene ring: it is twisted relative to the benzene ring by an angle of only 1.5 (1)°.

In the crystal structure, the inversely oriented molecules are arranged in double (A,A') columns, along the b axis, and linked by a network of intermolecular O–H···O (Aakeröy et al., 1992) hydrogen bonds (between A and A') and C–H···π (Takahashi et al., 2001) contacts (within A or A') (Table 1, Figs. 2 and 3). The 4H-chromene cores are parallel within A or A', but lie at an angle of 88.6 (1)° between A and A'. The crystal lattice is stabilized by dispersive interactions between inversely oriented columns. The intramolecular O11–H11···O12 hydrogen bond (Table 1, Figs. 1–3) is believed to be involved in the ESIPT phenomenon, characteristic of flavonols (Sengupta & Kasha, 1979).

Experimental

The title compound was synthesized as a result of the oxidative heterocyclization of 1-(2-hydroxyphenyl)-3-(4-methoxyphenyl)prop-2-en-1-one, synthesized first by the condensation of 1-(2-hydroxyphenyl)ethanone with 4-methoxybenzaldehyde in ethanol/50% aqueous NaOH (1/1 v/v), in alkaline ethanol/H₂O₂ (Sobottka et al., 2000). The filtered product was purified chromatographically (Silica Gel, chloroform/ethanol, 20/1 v/v) and colorless crystals suitable for X-ray investigations were grown from chloroform (m.p. = 510 – 511 K).