1-(3-Chloro­phen­yl)-5-(2,4-di­hydroxy­benzo­yl)pyridin-2(1H)-one

Fang Ren; Guifeng Li; Quanying Zhang; Jinhua Yao; Xuli Zhang

doi:10.1107/S1600536813009689

. 2013 Apr 13;69(Pt 5):o732. doi: 10.1107/S1600536813009689

1-(3-Chlorophenyl)-5-(2,4-dihydroxybenzoyl)pyridin-2(1H)-one

Fang Ren ^a,^*, Guifeng Li ^a, Quanying Zhang ^a, Jinhua Yao ^a, Xuli Zhang ^a

PMCID: PMC3648264 PMID: 23723884

Abstract

The chlorophenyl group of the title compound, C₁₈H₁₂ClNO₄, is disordered over two orientations with occupancies of 0.331 (8) and 0.669 (8). An intramolecular hydrogen bond is formed between a hydroxy group and the acyclic carbonyl group. In the crystal, molecules are linked into chains along [110] by O—H⋯O and C—H⋯O hydrogen bonds, forming a ladder motif.

Related literature

For similar structures, see: Ravinder et al. (2012 ▶); Sengupta et al. (2012 ▶). For the synthesis, see: Chen et al. (2011 ▶); Kim & Hong (2011 ▶). For the biological activity of similar structures, see: Kim et al. (2010 ▶). graphic file with name e-69-0o732-scheme1.jpg

Experimental

Crystal data

C₁₈H₁₂ClNO₄
M _r = 341.74
Triclinic,
a = 6.689 (3) Å
b = 9.009 (4) Å
c = 13.257 (6) Å
α = 87.193 (5)°
β = 87.719 (5)°
γ = 82.674 (5)°
V = 791.0 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.15 × 0.12 × 0.05 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.962, T _max = 0.987
3286 measured reflections
2726 independent reflections
1929 reflections with I > 2σ(I)
R _int = 0.049

Refinement

R[F ² > 2σ(F ²)] = 0.078
wR(F ²) = 0.233
S = 1.00
2726 reflections
236 parameters
48 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(21.8KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009689/fy2085sup1.cif

e-69-0o732-sup1.cif^{(21.8KB, cif)}

Click here for additional data file.^{(10.6KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536813009689/fy2085Isup2.cdx

Click here for additional data file.^{(133.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009689/fy2085Isup3.hkl

e-69-0o732-Isup3.hkl^{(133.8KB, hkl)}

Click here for additional data file.^{(5.8KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813009689/fy2085Isup4.cml

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
O2—H2⋯O3	0.91 (4)	1.75 (4)	2.587 (3)	152 (3)
O1—H1⋯O4ⁱ	0.87 (5)	1.79 (5)	2.655 (3)	175 (4)
C3—H3⋯O4ⁱ	0.93	2.50	3.165 (3)	129
C15—H15⋯O1ⁱⁱ	0.93	2.71	3.37 (2)	129

Open in a new tab

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

Acknowledgments

We are grateful to Attending Physician Tongqin Hao (The First Affiliated Hospital of Xinxiang Medical University, Henan, China) for the assistance with the antitumor assay.

supplementary crystallographic information

Comment

The title compound was prepared during our ongoing research on anticancer compounds. It is one of a limited number of reported crystal structures of 2-pyridone derivatives. The structure was confirmed by X-ray crystallography as shown in Fig. 1. H-bonding interactions play a decisive role in the crystal packing arrangement (Fig. 2). Intermolecular C3—H3···O4 and O1—H1···O4 contacts form a supramolecular chain parallel with [110]. Pairs of these chains are linked via C15—H15···O1 interactions to form a ladder motif.

Experimental

A solution of 7-methoxy-chromen-4-one (0.015 mol) in methanol (150 ml) was added dropwise to a solution of piperidine (0.030 mol) and rufluxed for 3 h at 0°C to get a crude product. This was added dropwise to a solution of dichloromethane (150 ml) and I₂ for an overnight reaction to give 3-iodo-7-methoxy-chromen-4-one with a 70% yield. Another 100 ml round-bottom flask fitted with mechanical stirrer was loaded with a mixture of 75 ml DMF and 5 ml water, then 3-iodo-7-methyloxy-4 H-chromone (3.0 g, 0.010 mol), methyl acrylate (1.2 g, 0.015 mol), Pd(Ph₃P)₂Cl₂ (0.07 g, 0.1 mmol), CuI (0.19 g, 10 mmol), and K₂CO₃ (1.38 g, 0.01 mol) were added successively. The mixture was heated to 70°C and stirred for 4 h. Then the mixture was filtered. The filtrate was poured into 100 ml of ice-water and then extracted with EtOAc. The extract was washed with saturated NaCl solution, dried over anhydrous MgSO₄, and concentrated to a volume of approximately 30 ml. The target compound 3-(7-methoxy-4-oxo-4H-chromen-3-yl)acrylic acid methyl ester was collected after the concentrated solution was cooled down to 4°C and maintained overnight (2.1 g, 76%). The solution of 3-(7-methoxy-4-oxo-4H-chromen-3-yl)acrylic acid methyl ester (1.04 g, 0.004 mol), 4-chlorophenylamine (0.41 g, 0.0044 mol), and triethylamine (3 drops) in MeOH (45 ml) was stirred under reflux for 8 h. After the mixture was cooled to room temperature and the solvent removed, the crude product was purified by chromatography over silica gel to give 1-(4-chlorophenyl)-5-(2-hydroxy-4-methoxy-benzoyl)-1H-pyridin-2-one with a yield of 72%. Then a solution of NaOH (0.004 mol) in water (5 ml) was added dropwise to a solution of 1-(4-chlorophenyl)-5-(2-hydroxy-4-methoxy-benzoyl)-1H-pyridin-2-one (0.003 mol) in ethanol (50 ml). Reaction at room temperature for 10 min gave the crude compound, which was recrystallized to obtain the title compound, 1-(4-chlorophenyl)-5-(2,4-dihydroxybenzoyl)-1H-pyridin-2-one. The recrystallized product was dissolved in EtOAc (1.5 ml) in an ampoule and PE (1.5 ml) was added dropwise. The ampoule was placed in refrigerator and single crystals were obtained by slow evaporation of the solvent (0.3 g, 35%; m.p. 391 K).