Crystal structure of (2-hy­droxy-5-methyl­phen­yl)(3-methyl-1-phenyl-1H-pyrazolo­[3,4-b]pyridin-5-yl)methanone

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

doi:10.1107/S2056989015011597

. 2015 Jun 24;71(Pt 7):o501–o502. doi: 10.1107/S2056989015011597

Crystal structure of (2-hydroxy-5-methylphenyl)(3-methyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-5-yl)methanone

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

PMCID: PMC4518926 PMID: 26279931

Abstract

In the title compound, C₂₁H₁₇N₃O₂, the 2-hydroxy-5-methylphenyl ring and the phenyl ring are inclined to the mean plane of the pyrazolopyridine moiety (r.m.s. deviation = 0.013 Å) by 52.89 (9) and 19.63 (8)°, respectively, and to each other by 42.83 (11)°. In the molecule, there are intramolecular O—H⋯O and C—H⋯N hydrogen bonds, both enclosing an S(6) ring motif. In the crystal, molecules stack along the c-axis direction, forming columns within which there are a number of π–π interactions [the inter-centroid distances vary from 3.5278 (10) to 3.8625 (10) Å]. The columns are linked by C—H⋯π interactions, forming slabs parallel to (100).

Keywords: crystal structure, pyrazoles, propenones, pyrazolopyridine, intramolecular hydrogen bonding, π–π interactions, C—H⋯π interactions

Related literature

For some details of the biological activity of pyrazole derivatives, see: Burger & Iorio (1979 ▸, 1980 ▸); Kalluraya & Ramesh (2001 ▸); Windholz (2003 ▸). For the antibacterial activity of propenones, see: Holla et al. (1994 ▸). For details of the pyrazole moiety found in blockbuster drugs, see: Penning et al. (1997 ▸) for celecobix; Terrett et al. (1996 ▸) for sildenafil; Seltzman et al. (1995 ▸) for rimonabant. graphic file with name e-71-0o501-scheme1.jpg

Experimental

Crystal data

C₂₁H₁₇N₃O₂
M _r = 343.38
Monoclinic,
a = 14.7164 (7) Å
b = 16.7306 (9) Å
c = 7.0733 (3) Å
β = 94.857 (2)°
V = 1735.29 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▸) T _min = 0.979, T _max = 0.983
10536 measured reflections
3055 independent reflections
2001 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.125
S = 1.04
3055 reflections
237 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 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/S2056989015011597/su5154sup1.cif

e-71-0o501-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015011597/su5154Isup2.hkl

e-71-0o501-Isup2.hkl^{(149.9KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015011597/su5154Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015011597/su5154fig1.tif

The molecular structure of the title compound, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. Intramolecular hydrogen bonds are shown as dashed lines (see Table 1 for details)

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

c . DOI: 10.1107/S2056989015011597/su5154fig2.tif

The crystal packing of the title compound, viewed along the c axis. The O—H⋯O and C—H⋯π interactions are shown as dashed lines (see Table 1 for details).

CCDC reference: 1406889

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

Table 1. Hydrogen-bond geometry (, ).

Cg3 and Cg4 are the centroids of rings C1C4/C6/C7 and C16C21, respectively.

DHA	DH	HA	D A	DHA
O1H1O2	0.82	1.91	2.613(2)	143
C21H21N1	0.93	2.41	3.019(3)	123
C5H5A Cg3ⁱ	0.96	2.97	3.703(3)	134
C20H20Cg4ⁱ	0.93	2.80	3.608(2)	146

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Department of Chemistry, IIT, Chennai, India, for the X-ray intensity data collection.

supplementary crystallographic information

S1. Comments

Pyrazole derivatives are reported to possess varied biological activities such as anti-inflammatory (Windholz, 2003), analgesic (Windholz, 2003), hypoglysemic, seditive (Burger et al., 1979), hypnotic (Burger et al., 1980), antifungal and antibacterial (Kalluraya & Ramesh, 2001) activities. Propenones are also found to show good antibacterial activity (Holla et al., 1994). The pyrazole moiety is found in blockbuster drugs such as celecobix (Penning et al., 1997), sildenafil (Terrett et al., 1996) and rimonabant (Seltzmann et al., 1995).

The molecular structure of the title molecule is shown in Fig. 1. The 2-hydroxy-5-methylphenyl ring (C1—C4/C6/C7) and the phenyl ring (C16—C21) are inclined to the mean plane of the pyrazolopyridine moiety (N1—N3/C9—C14; r.m.s. deviation = 0.013 Å) by 52.89 (9) and 19.63 (8) °, respectively, and to each other by 42.83 (11) °. The molecular conformation is partly determined by the intramolecular O—H···O hydrogen bond with an S(6) ring motif, and a C—H···N short contact enclosing a second S(6) ring motif (Table 1 and Fig. 1).

In the crystal, the molecules stack along the c axis direction forming columns, within which there are a number of π–π interactions [Cg1···Cg1ⁱ = 3.7660 (10) Å, interplanar distance = 3.4748 (7) Å, slippage = 1.452 Å; Cg1··· Cg1ⁱⁱ = 3.5278 (10) Å, interplanar distance = 3.4477 (7) Å, slippage = 0.747 Å; Cg1···Cg2ⁱ = 3.6162 (10) Å; Cg1···Cg2ⁱⁱ = 3.8625 (10) Å; Cg1 and Cg2 are the centroids of rings N2/N3/C11—C14 and N1/C9—C13, respectively; symmetry codes: (i) -x + 1, -y, -z; (ii) -x + 1, -y, -z + 1]. The columns are linked by C—H···π interactions (Table 1 and Fig. 2) forming slabs parallel to (100).

S2. Synthesis and crystallization

To a mixture of 3-formylchromone and 5-amino-3-methyl-1-phenyl pyrazole in ethanol, was added a catalytic amount of In(OTf)₃ and the resulting mixture was refluxed for ca. 20 min. The precipitate formed was filtered and dried under vacuum to afford the pure title product (yield: 87%). It was recrystallized from ethanol and DMSO-D₆ by slow evaporation over 48 h, giving colourless block-like crystals.

S3. Refinement

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