Crystal structure of (2S/2R,3S/3R)-3-hydroxy-2-phenyl­chroman-4-one

Roumaissa Belguedj; Sofiane Bouacida; Hocine Merazig; Aissa Chibani; Abdelmalek Bouraiou

doi:10.1107/S2056989015001346

. 2015 Jan 28;71(Pt 2):o131–o132. doi: 10.1107/S2056989015001346

Crystal structure of (2S/2R,3S/3R)-3-hydroxy-2-phenylchroman-4-one

Roumaissa Belguedj ^a, Sofiane Bouacida ^a,^b,^*, Hocine Merazig ^a, Aissa Chibani ^a, Abdelmalek Bouraiou ^a

PMCID: PMC4384603 PMID: 25878868

Abstract

In the title molecule, C₁₅H₁₂O₃, the C atoms bearing the hydroxy group and the phenyl ring are disordered over two sets of sites with refined occupancies of 0.573 (7) and 0.427 (7). There is also disorder of the phenyl ring but the hydroxy group was refined as ordered. The dihedral angles between the benzene ring of the chromane ring system and the phenyl ring are 89.7 (2)° for the major component of disorder and 72.1 (3)° for the minor component. Both disorder components of the the dihydropyran ring are in a half-chair conformation. In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers with an R ₂ ²(10) graph-set motif. Weak C—H⋯π interactions link these dimers into ladders along [001].

Keywords: crystal structure, flavone derivative, hydrogen bonds, C—H⋯π interactions

Related literature

For the synthesis and applications of flavone derivatives, see: Gaspar et al. (2014 ▸); Huang et al. (2007 ▸); Yu et al. (2003 ▸); Phosrithong et al. (2012 ▸); Harborne & Williams (2000 ▸); Tanaka & Sugino (2001 ▸); Saxena et al. (1985 ▸). For the synthesis of the title compound, see: Juvale et al. (2013 ▸). For a related structure, see: Piaskowska et al. (2013 ▸). graphic file with name e-71-0o131-scheme1.jpg

Experimental

Crystal data

C₁₅H₁₂O₃
M _r = 240.25
Monoclinic,
a = 5.3068 (3) Å
b = 26.7110 (18) Å
c = 9.4679 (6) Å
β = 117.431 (3)°
V = 1191.18 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.16 × 0.11 × 0.08 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2002 ▸) T _min = 0.615, T _max = 0.745
6701 measured reflections
2356 independent reflections
1517 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.148
S = 1.06
2356 reflections
216 parameters
30 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▸); cell refinement: SAINT (Bruker, 2011 ▸); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: WinGX (Farrugia, 2012 ▸).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015001346/lh5747sup1.cif

e-71-0o131-sup1.cif^{(28.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015001346/lh5747Isup2.hkl

e-71-0o131-Isup2.hkl^{(113.4KB, hkl)}

Click here for additional data file.^{(4.6KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015001346/lh5747Isup3.cml

Click here for additional data file.^{(1.3MB, tif)}

. DOI: 10.1107/S2056989015001346/lh5747fig1.tif

The molecule structure of the title compound. Displacement are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radius. The minor component of disorder is not shown.

Click here for additional data file.^{(1.7MB, tif)}

. DOI: 10.1107/S2056989015001346/lh5747fig2.tif

Part of the crystal structure of the title compound with hydrogen bonds shown as dashed lines and C—H⋯π intectations as green unbroken lines. The minor component of disorder is not shown.

CCDC reference: 1044756

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (, ).

Cg1 and Cg2 are the centroids of the C10C15 and C10AC15A rings, respectively.

DHA	DH	HA	D A	DHA
O3H3OO2ⁱ	0.89(4)	2.04(4)	2.856(3)	153(4)
C3H3A Cg1ⁱⁱ	0.93	2.74	3.596(5)	153
C3H3A Cg2ⁱⁱ	0.93	2.92	3.756(5)	151

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

Acknowledgments

Thanks are due to MESRS and the DG–RSDT (Ministére de l’Enseignement Supérieur et de la Recherche Scientifique et la Direction Générale de la Recherche - Algérie) for financial support.

supplementary crystallographic information

S1. Comment

Flavonoids are natural products derived from secondary metabolism of plants and play an important role in various biological processes (Harborne & Williams, 2000). All classes of flavonoids exhibit a variety of biological activities (Gaspar et al., 2014; Huang et al., 2007; Yu et al., 2003; Phosrithong et al., 2012). On the other hand, the Algar, Flynn and Oyamada (AFO) oxidation of substituted 2'-hydroxychalcones with alkaline hydrogen peroxide give flavonol derivatives (Juvale et al., 2013). Dihydroflavonol was also obtained by this reaction (Saxena et al., 1985; Tanaka & Sugino (2001). In this paper, we report the structure determination of the title compound resulting from the oxidation of 2'-hydroxychalcone using AFO reaction conditions.

The molecular structure of the title compound is shown in Fig. 1. The carbon atoms [C8 and C9] bearing the hydroxy group and the phenyl ring are disordered over two sets of sites with refined occupancies 0.573 (7) and 0.427 (7). This causes disorder of the phenyl ring [C10–C15] but the hydroxy group was refined as ordered. Atom O3 and the attached hydrogen atom occupy a single site. The dihedral angles between the benzene ring of the chromane ring system [C1–C6] and the phenyl ring are 89.7 (2)° for the major component of disorder [C10–C15] and 72.1 (3) for the minor component of disorder [C10A–C15A]. Both disorder components of the the dihydropyran are ring in a half-chair conformation. This type of geometry is comparable a published structure with a similar type of disorder (Piaskowska et al., 2013).

In the crystal, pairs of molecules are linked by O—H···O hydrogen bonds (Table 1), forming inversion dimers with R₂²(10) graph set motif. Weak C—H···pi interactions link these dimers into ladders along [001] (Fig. 2).

S2. Experimental

The title compound was obtained by subjecting the (E)-1-(2-hydroxyphenyl)-3-phenylprop-2-en-1-one to Algar-Flynn-Oymanda (AFO) conditions using aqueous hydrogen peroxide in the presence of sodium hydroxide. Colorless crystals of the title compound I with melting point: 449–251 K (yield: 52%) were grown by slow evaporation of a solution of the title compound in diethylether. The 1H NMR spectra is in full agreement with the proposed structure (Tanaka & Sugino, 2001). The relative position of the hydroxyl and phenyl ring on the new heterocyclic ring could not be determined efficiently by NMR spectroscopy (J H2—H3 ≈ 12.4 Hz). However, the X-ray structure determination revealed a trans-configuration.