organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

3,4,6-Tri­methyl-1-phenyl-1H-pyrazolo­[3,4-b]pyridine

aLaboratoire de Chimie Organique et Analytique, Equipe COOA, Faculté des Sciences et Techniques, Université Sultan Moulay Slimane, BP 523, 23000 Beni-Mellal, Morocco, bLaboratoires de Diffraction des Rayons X, Centre Nationale pour la Recherche Scientifique et Technique, Rabat, Morocco, and cLaboratoire de Biochimie, Environnement et Agroalimentaire (URAC 36), Faculté des Sciences et Techniques Mohammedia, Université Hassan II Mohammedia-Casablana, BP 146, 20800 Mohammedia, Morocco
*Correspondence e-mail: lazar_said@yahoo.fr

(Received 1 July 2010; accepted 5 July 2010; online 10 July 2010)

In the title compound, C15H15N3, the 1H-pyrazolo­[3,4-b]pyridine system and the phenyl ring are each individually planar, with r.m.s. deviations of 0.017 (2) and 0.011 (2) Å, respectively; the dihedral angle between the two aromatic systems is 9.33 (10)°. The crystal packing is stabilized by offset ππ stacking between parallel pyrazolo­[3,4-b]pyridine ring systems [face-to-face distance = 3.449 (6) Å].

Related literature

For a general review of pyrazolo­pyridines, see: Hardy (1984[Hardy, C. R. (1984). Heterocycl. Chem. 36, 343-409.]). For related compounds displaying biological activity, see: Chu & Lynchj (1975[Chu, I. & Lynchj, B. M. (1975). J. Med. Chem. 18, 161-165.]). For bond-length data, see: Allen et al. (1987[Allen, F. H., Kennard, O., Watson, D. G., Brammmer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1-19.]).

[Scheme 1]

Experimental

Crystal data
  • C15H15N3

  • Mr = 237.30

  • Monoclinic, P 21 /n

  • a = 7.1714 (2) Å

  • b = 12.0690 (4) Å

  • c = 14.5491 (5) Å

  • β = 101.251 (1)°

  • V = 1235.05 (7) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 296 K

  • 0.32 × 0.29 × 0.12 mm

Data collection
  • Bruker X8 APEXII CCD area-detector diffractometer

  • 10642 measured reflections

  • 2252 independent reflections

  • 1841 reflections with I > 2σ(I)

  • Rint = 0.029

Refinement
  • R[F2 > 2σ(F2)] = 0.068

  • wR(F2) = 0.198

  • S = 1.09

  • 2252 reflections

  • 166 parameters

  • H-atom parameters constrained

  • Δρmax = 0.74 e Å−3

  • Δρmin = −0.26 e Å−3

Data collection: APEX2 (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2005[Bruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]); software used to prepare material for publication: publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Supporting information


Comment top

Many polysubstituted derivatives of 1 H-pyrazolo[3,4-b]pyridine have been synthesized as potentially biologically active materials (Hardy, 1984; Chu & Lynchj, 1975).

The dihedral angle between the two aromatic ring systems in the title compound, C15H15N3, is 9.33 (10)°. The 1H-pyrazolo[3,4-b]pyridine and the phenyl rings are planarswith r.m.s. deviation of 0.017 (2) and 0.011 (2) Å, respectively.

The Bond lengths and angles in title compound (Fig. 1) are found to have normal values [Allen et al., 1987]. The crystal packing is stabilized by offset π-π stacking between parallel pyrazolo[3,4-b]pyridine ring sestems related by an inversion center at 1.0, 0.5, 0.0, the face-to-face distance is 3.449 (6) Å.

Related literature top

For a general review of pyrazolopyridines, see: Hardy (1984). For related compounds displaying biological activity, see: Chu & Lynchj (1975). For bond-length data, see: Allen et al. (1987).

Experimental top

To a solution of 4-hydroxy-6-methylpyran-2-one (291 mg, 2.309 mmol) and 5-amino-3-methyl-1-phenylpyrazole (200 mg, 1.154 mmol) in 10 ml of n-butanol was added p-toluenesulfonic acid (0.12 mg).

The reaction mixture was refluxed for 42 h. After evaporation of solvent, the residue was then purified over silica gel column chromatography using a (98:2) mixture of hexane and ethyl acetate as eluent. Under these conditions the compound was obtained as colourless crystals.

Refinement top

All H atoms were fixed geometrically and treated as riding with C—H = 0.96 Å (methyl) and C—H = 0.93 Å (aromatic), Uiso(H) = 1.5Ueq(C) for methyl and Uiso(H) = 1.2Ueq(C) for the others.

Structure description top

Many polysubstituted derivatives of 1 H-pyrazolo[3,4-b]pyridine have been synthesized as potentially biologically active materials (Hardy, 1984; Chu & Lynchj, 1975).

The dihedral angle between the two aromatic ring systems in the title compound, C15H15N3, is 9.33 (10)°. The 1H-pyrazolo[3,4-b]pyridine and the phenyl rings are planarswith r.m.s. deviation of 0.017 (2) and 0.011 (2) Å, respectively.

The Bond lengths and angles in title compound (Fig. 1) are found to have normal values [Allen et al., 1987]. The crystal packing is stabilized by offset π-π stacking between parallel pyrazolo[3,4-b]pyridine ring sestems related by an inversion center at 1.0, 0.5, 0.0, the face-to-face distance is 3.449 (6) Å.

For a general review of pyrazolopyridines, see: Hardy (1984). For related compounds displaying biological activity, see: Chu & Lynchj (1975). For bond-length data, see: Allen et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top
[Figure 1] Fig. 1. Molecular structure of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small spheres of arbitrary radii.
3,4,6-Trimethyl-1-phenyl-1H-pyrazolo[3,4-b]pyridine top
Crystal data top
C15H15N3F(000) = 504
Mr = 237.30Dx = 1.276 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1348 reflections
a = 7.1714 (2) Åθ = 2.6–25.5°
b = 12.0690 (4) ŵ = 0.08 mm1
c = 14.5491 (5) ÅT = 296 K
β = 101.251 (1)°Prism, colourless
V = 1235.05 (7) Å30.32 × 0.29 × 0.12 mm
Z = 4
Data collection top
Bruker X8 APEXII CCD area-detector
diffractometer
1841 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.029
Graphite monochromatorθmax = 25.3°, θmin = 2.9°
φ and ω scansh = 78
10642 measured reflectionsk = 1414
2252 independent reflectionsl = 1717
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.068Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.198H-atom parameters constrained
S = 1.09 w = 1/[σ2(Fo2) + (0.104P)2 + 1.0638P]
where P = (Fo2 + 2Fc2)/3
2252 reflections(Δ/σ)max < 0.001
166 parametersΔρmax = 0.74 e Å3
0 restraintsΔρmin = 0.26 e Å3
Crystal data top
C15H15N3V = 1235.05 (7) Å3
Mr = 237.30Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.1714 (2) ŵ = 0.08 mm1
b = 12.0690 (4) ÅT = 296 K
c = 14.5491 (5) Å0.32 × 0.29 × 0.12 mm
β = 101.251 (1)°
Data collection top
Bruker X8 APEXII CCD area-detector
diffractometer
1841 reflections with I > 2σ(I)
10642 measured reflectionsRint = 0.029
2252 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0680 restraints
wR(F2) = 0.198H-atom parameters constrained
S = 1.09Δρmax = 0.74 e Å3
2252 reflectionsΔρmin = 0.26 e Å3
166 parameters
Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
C10.8454 (3)0.7445 (2)0.04712 (18)0.0367 (6)
C20.7992 (4)0.6928 (2)0.13595 (19)0.0421 (7)
C30.7465 (3)0.5818 (2)0.14607 (17)0.0332 (6)
C40.7468 (3)0.5266 (2)0.06073 (18)0.0351 (6)
C50.7917 (3)0.5850 (2)0.02285 (17)0.0316 (6)
C60.9021 (4)0.8635 (2)0.0425 (2)0.0472 (7)
C70.6952 (4)0.5279 (3)0.23948 (19)0.0492 (8)
C80.7099 (3)0.4171 (2)0.0326 (2)0.0380 (7)
C90.6593 (4)0.3137 (3)0.0909 (2)0.0481 (8)
C100.8125 (3)0.5303 (2)0.19304 (17)0.0317 (6)
C110.8164 (3)0.4380 (2)0.24944 (19)0.0378 (6)
C120.8416 (4)0.4501 (2)0.3447 (2)0.0404 (7)
C130.8649 (4)0.5527 (2)0.38535 (18)0.0362 (6)
C140.8657 (4)0.6457 (2)0.33032 (18)0.0356 (6)
C150.8396 (3)0.6356 (2)0.23326 (18)0.0355 (6)
N10.8420 (3)0.69504 (17)0.03365 (15)0.0339 (5)
N20.7298 (3)0.41044 (18)0.05772 (16)0.0380 (6)
N30.7801 (3)0.51439 (17)0.09427 (15)0.0332 (5)
H110.80190.36770.22280.045*
H120.84280.38770.38230.048*
H130.88020.55970.45010.043*
H140.88380.71530.35810.043*
H150.84010.69800.19580.043*
H20.80420.73430.18930.051*
H6A0.79310.90850.06650.071*
H6B0.99750.87500.07960.071*
H6C0.95230.88350.02140.071*
H7A0.70680.58060.28740.074*
H7B0.56660.50160.24880.074*
H7C0.77920.46660.24250.074*
H9A0.76620.29130.11730.072*
H9B0.55290.32880.14050.072*
H9C0.62680.25540.05200.072*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0326 (13)0.0418 (15)0.0371 (14)0.0062 (11)0.0100 (11)0.0020 (11)
C20.0459 (15)0.0491 (17)0.0334 (15)0.0081 (12)0.0129 (12)0.0066 (12)
C30.0279 (12)0.0443 (15)0.0284 (13)0.0109 (10)0.0075 (10)0.0000 (11)
C40.0274 (12)0.0418 (15)0.0358 (14)0.0058 (10)0.0055 (10)0.0037 (11)
C50.0251 (11)0.0406 (14)0.0302 (13)0.0069 (10)0.0082 (9)0.0044 (10)
C60.0545 (17)0.0469 (17)0.0440 (17)0.0002 (13)0.0191 (13)0.0156 (13)
C70.0453 (16)0.068 (2)0.0342 (15)0.0045 (14)0.0065 (12)0.0091 (14)
C80.0257 (12)0.0334 (14)0.0554 (18)0.0045 (10)0.0092 (11)0.0069 (12)
C90.0431 (15)0.0554 (19)0.0420 (17)0.0041 (13)0.0011 (12)0.0138 (13)
C100.0224 (11)0.0444 (15)0.0279 (12)0.0048 (10)0.0041 (9)0.0043 (11)
C110.0367 (13)0.0302 (13)0.0470 (16)0.0026 (10)0.0096 (11)0.0034 (11)
C120.0430 (14)0.0353 (15)0.0445 (16)0.0020 (11)0.0127 (12)0.0116 (12)
C130.0400 (14)0.0445 (15)0.0238 (12)0.0081 (11)0.0050 (10)0.0046 (11)
C140.0422 (14)0.0296 (13)0.0338 (14)0.0040 (11)0.0044 (11)0.0049 (10)
C150.0394 (13)0.0338 (13)0.0333 (14)0.0079 (11)0.0072 (10)0.0114 (11)
N10.0322 (11)0.0275 (11)0.0444 (13)0.0041 (8)0.0134 (9)0.0057 (9)
N20.0374 (12)0.0295 (12)0.0460 (14)0.0025 (9)0.0053 (10)0.0084 (10)
N30.0373 (11)0.0284 (11)0.0339 (12)0.0010 (9)0.0068 (9)0.0026 (9)
Geometric parameters (Å, º) top
C1—C61.491 (4)C10—C111.380 (4)
C2—H20.9300C11—H110.9300
C2—C11.415 (4)C11—C121.370 (4)
C3—C71.487 (4)C12—H120.9300
C3—C41.408 (4)C13—H130.9300
C3—C21.392 (4)C13—C141.379 (4)
C4—C81.424 (4)C13—C121.368 (4)
C4—C51.388 (4)C14—H140.9300
C6—H6C0.9600C15—H150.9300
C6—H6B0.9600C15—C101.397 (4)
C6—H6A0.9600C15—C141.393 (4)
C7—H7C0.9600N1—C51.377 (3)
C7—H7B0.9600N1—C11.322 (3)
C7—H7A0.9600N2—N31.383 (3)
C8—C91.512 (4)N2—C81.296 (4)
C9—H9C0.9600N3—C101.423 (3)
C9—H9B0.9600N3—C51.359 (3)
C9—H9A0.9600
C1—C6—H6C109.5C12—C13—C14119.9 (2)
C1—C6—H6B109.5C12—C11—H11120.0
C1—C6—H6A109.5C12—C11—C10119.9 (2)
C1—C2—H2118.9C13—C12—H12119.5
C1—N1—C5112.6 (2)C13—C12—C11121.0 (2)
C2—C1—C6118.6 (2)C13—C14—H14119.9
C2—C3—C7122.1 (2)C13—C14—C15120.2 (2)
C2—C3—C4114.1 (2)C14—C13—H13120.0
C3—C7—H7C109.5C14—C15—H15120.5
C3—C7—H7B109.5C14—C15—C10119.0 (2)
C3—C7—H7A109.5C15—C14—H14119.9
C3—C2—H2118.9C15—C10—N3121.8 (2)
C3—C2—C1122.1 (2)H6A—C6—H6C109.5
C3—C4—C8136.4 (3)H6A—C6—H6B109.5
C4—C8—C9130.0 (3)H6B—C6—H6C109.5
C4—C3—C7123.8 (3)H7A—C7—H7C109.5
C5—C4—C8104.1 (2)H7A—C7—H7B109.5
C5—C4—C3119.5 (3)H7B—C7—H7C109.5
C5—N3—C10131.7 (2)H9A—C9—H9C109.5
C5—N3—N2109.0 (2)H9A—C9—H9B109.5
C8—C9—H9C109.5H9B—C9—H9C109.5
C8—C9—H9B109.5N1—C1—C6116.6 (2)
C8—C9—H9A109.5N1—C1—C2124.8 (3)
C8—N2—N3107.6 (2)N1—C5—C4126.9 (2)
C10—C11—H11120.0N2—C8—C9119.0 (2)
C10—C15—H15120.5N2—C8—C4111.0 (2)
C11—C12—H12119.5N2—N3—C10119.3 (2)
C11—C10—N3118.2 (2)N3—C5—C4108.2 (2)
C11—C10—C15120.0 (2)N3—C5—N1124.8 (2)
C12—C13—H13120.0

Experimental details

Crystal data
Chemical formulaC15H15N3
Mr237.30
Crystal system, space groupMonoclinic, P21/n
Temperature (K)296
a, b, c (Å)7.1714 (2), 12.0690 (4), 14.5491 (5)
β (°) 101.251 (1)
V3)1235.05 (7)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.32 × 0.29 × 0.12
Data collection
DiffractometerBruker X8 APEXII CCD area-detector
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
10642, 2252, 1841
Rint0.029
(sin θ/λ)max1)0.601
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.068, 0.198, 1.09
No. of reflections2252
No. of parameters166
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.74, 0.26

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009), publCIF (Westrip, 2010).

 

Acknowledgements

The authors thank the CNRST of Morocco for making this work possible.

References

First citationAllen, F. H., Kennard, O., Watson, D. G., Brammmer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.  CrossRef Google Scholar
First citationBruker (2005). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationChu, I. & Lynchj, B. M. (1975). J. Med. Chem. 18, 161–165.  CrossRef PubMed CAS Web of Science Google Scholar
First citationHardy, C. R. (1984). Heterocycl. Chem. 36, 343–409.  CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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