Crystal structure of (5-chloro-2-hy­droxy­phen­yl)(3-methyl­isoxazolo[5,4-b]pyridin-5-yl)methanone

Rajamani Raja; Nataraj Poomathi; Paramasivam T Perumal; A SubbiahPandi

doi:10.1107/S2056989015019635

. 2015 Oct 24;71(Pt 11):o875–o876. doi: 10.1107/S2056989015019635

Crystal structure of (5-chloro-2-hydroxyphenyl)(3-methylisoxazolo[5,4-b]pyridin-5-yl)methanone

Rajamani Raja ^a, Nataraj Poomathi ^b, Paramasivam T Perumal ^b, A SubbiahPandi ^a,^*

PMCID: PMC4645069 PMID: 26594574

Abstract

In the title compound, C₁₄H₉ClN₂O₃, the fused pyridine and isoxazole rings are approximately planar, making a dihedral angle of 1.14 (16)°. The molecule is twisted with the benzene ring and the mean plane through the fused pyridine-isoxazole ring system being inclined to one another by 47.03 (13)°. There is an intramolecular O—H⋯O hydrogen bond forming an S(6) ring motif. In the crystal, molecules are linked by C—H⋯N hydrogen bonds, forming chains propagating along [001]. The chains are linked by slipped parallel π–π interactions, involving inversion-related benzene rings, forming slabs lying parallel to the bc plane {inter-centroid distance = 3.770 (2) Å].

Keywords: crystal structure, polyfunctional pyridines, isoxazole, O—H⋯O hydrogen bonds, C—H⋯N hydrogen bonds

Related literature

For various applications of polyfunctional pyridines, see: Knyazhanskii et al. (1996 ▸); Kürfurst et al. (1989 ▸); Enyedy et al. (2003 ▸); Arora & Knaus (1999 ▸); Kim et al. 2004 ▸); Pillai et al.(2003 ▸). graphic file with name e-71-0o875-scheme1.jpg

Experimental

Crystal data

C₁₄H₉ClN₂O₃
M _r = 288.68
Monoclinic,
a = 11.0317 (10) Å
b = 11.8701 (10) Å
c = 11.1220 (9) Å
β = 118.675 (2)°
V = 1277.78 (19) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.35 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.900, T _max = 0.927
17705 measured reflections
2250 independent reflections
1763 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.110
S = 1.13
2250 reflections
182 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▸); cell refinement: SAINT (Bruker, 2008 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▸).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989015019635/su5220sup1.cif

e-71-0o875-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015019635/su5220Isup2.hkl

e-71-0o875-Isup2.hkl^{(110.6KB, hkl)}

Click here for additional data file.^{(5.1KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015019635/su5220Isup3.cml

Click here for additional data file.^{(1.2MB, tif)}

. DOI: 10.1107/S2056989015019635/su5220fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.^{(2.1MB, tif)}

b- . DOI: 10.1107/S2056989015019635/su5220fig2.tif

A view along the b-axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details).

CCDC reference: 1431889

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

Table 1. Hydrogen-bond geometry (, ).

DHA	DH	HA	D A	DHA
O1H1O2	0.82	1.84	2.561(4)	145
C12H12N2ⁱ	0.93	2.40	3.315(4)	168

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Department of Chemistry, IIT, Chennai, India, for the data collection.

supplementary crystallographic information

S1. Chemical context

Poly-functional pyridines are an interesting class of compounds due to their optical properties (Knyazhanskii et al., 1996; Kürfurst et al., 1989), and their biological activities (Enyedy et al., 2003), such as anticonvulsants (Arora et al., 1999), antihistaminic reagents (Kim et al., 2004), and cardivascular disorder treatments (Pillai et al., 2003). In view of such facts we herein report on the synthesis and crystal structure of the new title poly-functional pyridine compound.

S2. Structural commentary

In the title compound, Fig. 1, the fused pyridine ring (N1/C8—C12) and isoxazole ring (O3/N2/C13/C11/C10) are almost coplanar being inclined to one another by 1.14 (16) °. The molecule is twisted with the benzene ring (C1—C6) and the mean plane through the fused pyridine-isoxazole ring system being inclined to one another by 47.03 (13) °. The molecular conformation is partly determined by the intramolecular O—H···O hydrogen bond which forms an S(6) ring motif.

In the crystal, molecules are linked by C—H···N hydrogen bond to form chains propagating along the c axis direction (Table 1 and Fig. 2). The chains are linked by slipped parallel π—π interactions, involving inversion related 5-chloro-2-hydroxyphenyl rings, forming slabs parallel to the bc-plane; see Fig. 2 [Cg3—Cg3ⁱ = 3.770 (2) Å, inter-planar distance = 3.4094 (14) Å, slippage = 1.609 Å; Cg3 is the centroid of ring (C1—C6); symmetry code: (i) −x, −y, 2 − z].

S3. Synthesis and crystallization

To a mixture of 6-chloro-3-formylchromone (1 mmol) and 3-methylisoxazol-5-amine (1 mmol) in ethanol (3 ml) was added a catalytic amount (0.050 mmol) of In(OTf)₃ and the mixture was refluxed for about 20 min. The precipitated solid was filtered and dried under vacuum to afford the pure product in 87% yield. The purified compound was recrystallized from ethanol and DMSO-D₆ by slow evaporation giving colourless block-like crystals.

S4. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The OH and C-bound H atoms were positioned geometrically (O—H = 0.82 Å, C–H = 0.93–0.96 Å) and allowed to ride on their parent atoms, with U_iso(H) = 1.5U_eq(O,C) for hydroxyl and methyl H atoms and 1.2U_eq(C) for other H atoms.