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

Hamri, S.; Hafid, A.; Zouihri, H.; Lazar, S.; Khouili, M.

doi:10.1107/S1600536810026474

organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o1966

https://doi.org/10.1107/S1600536810026474

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

Salha Hamri,^a Abderrafia Hafid,^a Hafid Zouihri,^b Saïd Lazar ^c ^* and Mostafa Khouili ^a

^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 π–π 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 ). For related compounds displaying biological activity, see: Chu & Lynchj (1975 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₅H₁₅N₃
M_r = 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)
R_int = 0.029

Refinement

R[F² > 2σ(F²)] = 0.068
wR(F²) = 0.198
S = 1.09
2252 reflections
166 parameters
H-atom parameters constrained
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; 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 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536810026474/xu2793sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810026474/xu2793Isup2.hkl

checkCIF report

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.

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).

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

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

C₁₅H₁₅N₃	F(000) = 504
M_r = 237.30	D_x = 1.276 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1348 reflections
a = 7.1714 (2) Å	θ = 2.6–25.5°
b = 12.0690 (4) Å	µ = 0.08 mm⁻¹
c = 14.5491 (5) Å	T = 296 K
β = 101.251 (1)°	Prism, colourless
V = 1235.05 (7) Å³	0.32 × 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 tube	R_int = 0.029
Graphite monochromator	θ_max = 25.3°, θ_min = 2.9°
φ and ω scans	h = −7→8
10642 measured reflections	k = −14→14
2252 independent reflections	l = −17→17

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.198	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.104P)² + 1.0638P] where P = (F_o² + 2F_c²)/3
2252 reflections	(Δ/σ)_max < 0.001
166 parameters	Δρ_max = 0.74 e Å⁻³
0 restraints	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₅H₁₅N₃	V = 1235.05 (7) Å³
M_r = 237.30	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.1714 (2) Å	µ = 0.08 mm⁻¹
b = 12.0690 (4) Å	T = 296 K
c = 14.5491 (5) Å	0.32 × 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 reflections	R_int = 0.029
2252 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.068	0 restraints
wR(F²) = 0.198	H-atom parameters constrained
S = 1.09	Δρ_max = 0.74 e Å⁻³
2252 reflections	Δρ_min = −0.26 e Å⁻³
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

	x	y	z	U_iso*/U_eq
C1	0.8454 (3)	0.7445 (2)	−0.04712 (18)	0.0367 (6)
C2	0.7992 (4)	0.6928 (2)	−0.13595 (19)	0.0421 (7)
C3	0.7465 (3)	0.5818 (2)	−0.14607 (17)	0.0332 (6)
C4	0.7468 (3)	0.5266 (2)	−0.06073 (18)	0.0351 (6)
C5	0.7917 (3)	0.5850 (2)	0.02285 (17)	0.0316 (6)
C6	0.9021 (4)	0.8635 (2)	−0.0425 (2)	0.0472 (7)
C7	0.6952 (4)	0.5279 (3)	−0.23948 (19)	0.0492 (8)
C8	0.7099 (3)	0.4171 (2)	−0.0326 (2)	0.0380 (7)
C9	0.6593 (4)	0.3137 (3)	−0.0909 (2)	0.0481 (8)
C10	0.8125 (3)	0.5303 (2)	0.19304 (17)	0.0317 (6)
C11	0.8164 (3)	0.4380 (2)	0.24944 (19)	0.0378 (6)
C12	0.8416 (4)	0.4501 (2)	0.3447 (2)	0.0404 (7)
C13	0.8649 (4)	0.5527 (2)	0.38535 (18)	0.0362 (6)
C14	0.8657 (4)	0.6457 (2)	0.33032 (18)	0.0356 (6)
C15	0.8396 (3)	0.6356 (2)	0.23326 (18)	0.0355 (6)
N1	0.8420 (3)	0.69504 (17)	0.03365 (15)	0.0339 (5)
N2	0.7298 (3)	0.41044 (18)	0.05772 (16)	0.0380 (6)
N3	0.7801 (3)	0.51439 (17)	0.09427 (15)	0.0332 (5)
H11	0.8019	0.3677	0.2228	0.045*
H12	0.8428	0.3877	0.3823	0.048*
H13	0.8802	0.5597	0.4501	0.043*
H14	0.8838	0.7153	0.3581	0.043*
H15	0.8401	0.6980	0.1958	0.043*
H2	0.8042	0.7343	−0.1893	0.051*
H6A	0.7931	0.9085	−0.0665	0.071*
H6B	0.9975	0.8750	−0.0796	0.071*
H6C	0.9523	0.8835	0.0214	0.071*
H7A	0.7068	0.5806	−0.2874	0.074*
H7B	0.5666	0.5016	−0.2488	0.074*
H7C	0.7792	0.4666	−0.2425	0.074*
H9A	0.7662	0.2913	−0.1173	0.072*
H9B	0.5529	0.3288	−0.1405	0.072*
H9C	0.6268	0.2554	−0.0520	0.072*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0326 (13)	0.0418 (15)	0.0371 (14)	0.0062 (11)	0.0100 (11)	−0.0020 (11)
C2	0.0459 (15)	0.0491 (17)	0.0334 (15)	0.0081 (12)	0.0129 (12)	0.0066 (12)
C3	0.0279 (12)	0.0443 (15)	0.0284 (13)	0.0109 (10)	0.0075 (10)	0.0000 (11)
C4	0.0274 (12)	0.0418 (15)	0.0358 (14)	0.0058 (10)	0.0055 (10)	−0.0037 (11)
C5	0.0251 (11)	0.0406 (14)	0.0302 (13)	0.0069 (10)	0.0082 (9)	0.0044 (10)
C6	0.0545 (17)	0.0469 (17)	0.0440 (17)	0.0002 (13)	0.0191 (13)	0.0156 (13)
C7	0.0453 (16)	0.068 (2)	0.0342 (15)	0.0045 (14)	0.0065 (12)	−0.0091 (14)
C8	0.0257 (12)	0.0334 (14)	0.0554 (18)	0.0045 (10)	0.0092 (11)	0.0069 (12)
C9	0.0431 (15)	0.0554 (19)	0.0420 (17)	0.0041 (13)	−0.0011 (12)	−0.0138 (13)
C10	0.0224 (11)	0.0444 (15)	0.0279 (12)	0.0048 (10)	0.0041 (9)	−0.0043 (11)
C11	0.0367 (13)	0.0302 (13)	0.0470 (16)	−0.0026 (10)	0.0096 (11)	−0.0034 (11)
C12	0.0430 (14)	0.0353 (15)	0.0445 (16)	0.0020 (11)	0.0127 (12)	0.0116 (12)
C13	0.0400 (14)	0.0445 (15)	0.0238 (12)	0.0081 (11)	0.0050 (10)	0.0046 (11)
C14	0.0422 (14)	0.0296 (13)	0.0338 (14)	0.0040 (11)	0.0044 (11)	−0.0049 (10)
C15	0.0394 (13)	0.0338 (13)	0.0333 (14)	0.0079 (11)	0.0072 (10)	0.0114 (11)
N1	0.0322 (11)	0.0275 (11)	0.0444 (13)	0.0041 (8)	0.0134 (9)	0.0057 (9)
N2	0.0374 (12)	0.0295 (12)	0.0460 (14)	−0.0025 (9)	0.0053 (10)	−0.0084 (10)
N3	0.0373 (11)	0.0284 (11)	0.0339 (12)	−0.0010 (9)	0.0068 (9)	−0.0026 (9)

Geometric parameters (Å, º) top

C1—C6	1.491 (4)	C10—C11	1.380 (4)
C2—H2	0.9300	C11—H11	0.9300
C2—C1	1.415 (4)	C11—C12	1.370 (4)
C3—C7	1.487 (4)	C12—H12	0.9300
C3—C4	1.408 (4)	C13—H13	0.9300
C3—C2	1.392 (4)	C13—C14	1.379 (4)
C4—C8	1.424 (4)	C13—C12	1.368 (4)
C4—C5	1.388 (4)	C14—H14	0.9300
C6—H6C	0.9600	C15—H15	0.9300
C6—H6B	0.9600	C15—C10	1.397 (4)
C6—H6A	0.9600	C15—C14	1.393 (4)
C7—H7C	0.9600	N1—C5	1.377 (3)
C7—H7B	0.9600	N1—C1	1.322 (3)
C7—H7A	0.9600	N2—N3	1.383 (3)
C8—C9	1.512 (4)	N2—C8	1.296 (4)
C9—H9C	0.9600	N3—C10	1.423 (3)
C9—H9B	0.9600	N3—C5	1.359 (3)
C9—H9A	0.9600

C1—C6—H6C	109.5	C12—C13—C14	119.9 (2)
C1—C6—H6B	109.5	C12—C11—H11	120.0
C1—C6—H6A	109.5	C12—C11—C10	119.9 (2)
C1—C2—H2	118.9	C13—C12—H12	119.5
C1—N1—C5	112.6 (2)	C13—C12—C11	121.0 (2)
C2—C1—C6	118.6 (2)	C13—C14—H14	119.9
C2—C3—C7	122.1 (2)	C13—C14—C15	120.2 (2)
C2—C3—C4	114.1 (2)	C14—C13—H13	120.0
C3—C7—H7C	109.5	C14—C15—H15	120.5
C3—C7—H7B	109.5	C14—C15—C10	119.0 (2)
C3—C7—H7A	109.5	C15—C14—H14	119.9
C3—C2—H2	118.9	C15—C10—N3	121.8 (2)
C3—C2—C1	122.1 (2)	H6A—C6—H6C	109.5
C3—C4—C8	136.4 (3)	H6A—C6—H6B	109.5
C4—C8—C9	130.0 (3)	H6B—C6—H6C	109.5
C4—C3—C7	123.8 (3)	H7A—C7—H7C	109.5
C5—C4—C8	104.1 (2)	H7A—C7—H7B	109.5
C5—C4—C3	119.5 (3)	H7B—C7—H7C	109.5
C5—N3—C10	131.7 (2)	H9A—C9—H9C	109.5
C5—N3—N2	109.0 (2)	H9A—C9—H9B	109.5
C8—C9—H9C	109.5	H9B—C9—H9C	109.5
C8—C9—H9B	109.5	N1—C1—C6	116.6 (2)
C8—C9—H9A	109.5	N1—C1—C2	124.8 (3)
C8—N2—N3	107.6 (2)	N1—C5—C4	126.9 (2)
C10—C11—H11	120.0	N2—C8—C9	119.0 (2)
C10—C15—H15	120.5	N2—C8—C4	111.0 (2)
C11—C12—H12	119.5	N2—N3—C10	119.3 (2)
C11—C10—N3	118.2 (2)	N3—C5—C4	108.2 (2)
C11—C10—C15	120.0 (2)	N3—C5—N1	124.8 (2)
C12—C13—H13	120.0

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃
M_r	237.30
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.1714 (2), 12.0690 (4), 14.5491 (5)
β (°)	101.251 (1)
V (Å³)	1235.05 (7)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.29 × 0.12

Data collection
Diffractometer	Bruker X8 APEXII CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	10642, 2252, 1841
R_int	0.029
(sin θ/λ)_max (Å⁻¹)	0.601

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.068, 0.198, 1.09
No. of reflections	2252
No. of parameters	166
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	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

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