5-(Pyridin-4-ylmeth­yl)-1H-pyrazolo­[3,4-d]pyrimidin-4(5H)-one

Alsubari, A.; Ramli, Y.; Essassi, E.M.; Zouihri, H.

doi:10.1107/S1600536811025025

organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page o1926

doi:10.1107/S1600536811025025

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5-(Pyridin-4-ylmethyl)-1H-pyrazolo[3,4-d]pyrimidin-4(5H)-one

Abdulsalam Alsubari,^a ^* Youssef Ramli,^a El Mokhtar Essassi ^a and Hafid Zouihri ^b

^aLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, and ^bLaboratoires de Diffraction des Rayons X, Centre National pour la Recherche, Scientifique et Technique, Rabat, Morocco
^*Correspondence e-mail: abdalsalam_1977@hotmail.com

(Received 17 June 2011; accepted 25 June 2011; online 6 July 2011)

In the title compound, C₁₁H₉N₅O, the pyrazolopyrimidin-4-one ring system is almost planar, with a maximum deviation of 0.0546 (13) Å for the O atom. The crystal packing is stabilized by intermolecular N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds. In addition, π–π stacking is found between the pyridine ring and the pyrazolopyrimidin-4-one ring systems, with centroid–centroid distances in the range 3.9627 (12)–4.6781 (12) Å.

Related literature

For a related structure, see: Al Subari et al. (2010 ). For the biological activity of pyrazolopyrimidinone derivatives, see: Kim et al. (2001 ); Ali et al. (2009 ).

Experimental

Crystal data

C₁₁H₉N₅O
M_r = 227.23
Monoclinic, P 2₁
a = 4.6371 (3) Å
b = 19.2731 (10) Å
c = 5.8593 (3) Å
β = 102.498 (2)°
V = 511.24 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.17 mm

Data collection

Bruker APEXII CCD detector diffractometer
6285 measured reflections
2603 independent reflections
2201 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.085
S = 1.05
2603 reflections
158 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N5ⁱ	0.90 (2)	1.96 (2)	2.840 (2)	168 (2)
C4—H4⋯N4ⁱⁱ	0.93	2.61	3.526 (2)	167
C9—H9⋯N2ⁱⁱⁱ	0.93	2.36	3.289 (2)	174
C11—H11⋯O1^iv	0.93	2.52	3.430 (2)	167
Symmetry codes: (i) $[-x+2, y+{\script{1\over 2}}, -z+1]$ ; (ii) $[-x+1, y-{\script{1\over 2}}, -z]$ ; (iii) x-1, y, z-1; (iv) x+1, y, z+1.

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: 10.1107/S1600536811025025/fj2436sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025025/fj2436Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811025025/fj2436Isup3.cml

checkCIF report

Comment top

Pyrazolopyrimidinone derivatives have attracted the attention of numerous researchers over many years due to their important biological activities [Kim, et al. 2001 and Ali, et al. 2009].

In the title compound, C₁₁H₉N₅O, the 4H-pyrazolo[3,4-d]pyrimidin-4-one core is almost planar (maximum atomic deviation = 0.0546 (13) Å for the oxygen atom of the system) and makes a dihedral angle of 73.94 (7)° with the attached pyridin ring (maximum atomic deviation = 0.041 (18) Å of the nitrogen atom of the ring). The crystal packing is stabilized by N—H···O and C—H···N intermolecular H-bonds and π–π stacking between pyridin and pyrazolo ring systems [Cg to Cg distances = 4.6781 (12) Å to 3.9627 (12) Å].

Related literature top

For a related structure, see: Al Subari et al. (2010). For the biological activity of pyrazolopyrimidinone derivatives, see: Kim et al. (2001); Ali et al. (2009).

Experimental top

allopurinol (1 g, 7.4 mmol), 4-chloromethylpyridine (1.8 g, 14.7 mmol) and potassium carbonate (1.5 g, 11.2 mmol) with amount of catalytic tetra-n-butylammonium bromide were stirred in DMF (30 ml) for 72 h. The solid material was removed by filtration and the solvent evaporated under vacuum. Dichloromethane (20 ml) was added and the solution filtered. The solid product was purified by recrystallization from ethanol to afford white crystals in 60% yield.

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 view of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. Partial packing view showing the chain formed by N—H···O and C—H···N hydrogen bondings. H atoms not involved in hydrogen bonds have been omitted for clarity.

5-(Pyridin-4-ylmethyl)-1H-pyrazolo[3,4-d]pyrimidin- 4(5H)-one top

Crystal data top

C₁₁H₉N₅O	F(000) = 236
M_r = 227.23	D_x = 1.476 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 342 reflections
a = 4.6371 (3) Å	θ = 2.4–25.6°
b = 19.2731 (10) Å	µ = 0.10 mm⁻¹
c = 5.8593 (3) Å	T = 296 K
β = 102.498 (2)°	Prism, colourless
V = 511.24 (5) Å³	0.25 × 0.22 × 0.17 mm
Z = 2

Data collection top

Bruker APEXII CCD detector diffractometer	2201 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 28.9°, θ_min = 2.1°
ω and ϕ scans	h = −6→6
6285 measured reflections	k = −26→26
2603 independent reflections	l = −7→7

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)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0427P)² + 0.0014P] where P = (F_o² + 2F_c²)/3
2603 reflections	(Δ/σ)_max = 0.001
158 parameters	Δρ_max = 0.16 e Å⁻³
2 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₁H₉N₅O	V = 511.24 (5) Å³
M_r = 227.23	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.6371 (3) Å	µ = 0.10 mm⁻¹
b = 19.2731 (10) Å	T = 296 K
c = 5.8593 (3) Å	0.25 × 0.22 × 0.17 mm
β = 102.498 (2)°

Data collection top

Bruker APEXII CCD detector diffractometer	2201 reflections with I > 2σ(I)
6285 measured reflections	R_int = 0.030
2603 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	2 restraints
wR(F²) = 0.085	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.16 e Å⁻³
2603 reflections	Δρ_min = −0.22 e Å⁻³
158 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
N2	0.7680 (3)	1.03978 (7)	0.5859 (2)	0.0280 (3)
N1	0.3899 (3)	0.95388 (6)	0.5329 (2)	0.0242 (3)
N3	0.7129 (3)	1.11511 (7)	0.2529 (2)	0.0275 (3)
N5	0.8324 (3)	0.71619 (7)	0.6387 (3)	0.0326 (3)
N4	0.5292 (3)	1.12382 (7)	0.0394 (2)	0.0312 (3)
O1	0.0403 (3)	0.93783 (6)	0.1944 (2)	0.0343 (3)
C8	0.3807 (3)	1.03227 (8)	0.2246 (3)	0.0233 (3)
C11	0.6365 (3)	0.98760 (8)	0.6577 (3)	0.0257 (3)
H11	0.7155	0.9713	0.8075	0.031*
C10	0.6293 (3)	1.06125 (8)	0.3675 (3)	0.0235 (3)
C7	0.2488 (4)	0.97246 (8)	0.3022 (3)	0.0242 (3)
C1	0.4678 (3)	0.83113 (8)	0.6455 (3)	0.0250 (3)
C6	0.2764 (4)	0.89454 (8)	0.6453 (3)	0.0289 (4)
H6A	0.0764	0.8842	0.5626	0.035*
H6B	0.2708	0.9066	0.8050	0.035*
C2	0.6726 (4)	0.81124 (9)	0.8437 (3)	0.0298 (4)
H2	0.6926	0.8360	0.9825	0.036*
C5	0.4487 (4)	0.79196 (8)	0.4448 (3)	0.0322 (4)
H5	0.3130	0.8036	0.3087	0.039*
C4	0.6333 (4)	0.73540 (8)	0.4486 (3)	0.0351 (4)
H4	0.6181	0.7095	0.3125	0.042*
C9	0.3281 (4)	1.07419 (8)	0.0210 (3)	0.0286 (3)
H9	0.1735	1.0677	−0.1078	0.034*
C3	0.8469 (4)	0.75365 (9)	0.8304 (3)	0.0332 (4)
H3	0.9827	0.7404	0.9646	0.040*
H3N	0.869 (4)	1.1429 (12)	0.304 (4)	0.060 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0245 (7)	0.0290 (7)	0.0283 (7)	0.0012 (6)	0.0011 (6)	−0.0026 (6)
N1	0.0251 (6)	0.0209 (6)	0.0264 (7)	0.0009 (5)	0.0052 (5)	0.0002 (5)
N3	0.0274 (7)	0.0252 (7)	0.0290 (8)	−0.0025 (6)	0.0042 (6)	−0.0006 (6)
N5	0.0329 (8)	0.0251 (7)	0.0411 (9)	0.0029 (6)	0.0108 (7)	0.0017 (6)
N4	0.0343 (8)	0.0293 (7)	0.0288 (8)	0.0020 (6)	0.0045 (6)	0.0010 (6)
O1	0.0323 (6)	0.0308 (6)	0.0355 (7)	−0.0077 (5)	−0.0025 (5)	−0.0025 (5)
C8	0.0213 (7)	0.0222 (7)	0.0252 (8)	0.0027 (6)	0.0020 (6)	−0.0028 (6)
C11	0.0259 (8)	0.0267 (8)	0.0222 (8)	0.0053 (6)	0.0003 (6)	−0.0015 (6)
C10	0.0227 (7)	0.0215 (7)	0.0263 (8)	0.0017 (6)	0.0050 (6)	−0.0034 (6)
C7	0.0225 (7)	0.0223 (7)	0.0268 (8)	0.0032 (6)	0.0032 (6)	−0.0039 (6)
C1	0.0264 (8)	0.0221 (7)	0.0280 (8)	−0.0036 (6)	0.0096 (7)	0.0014 (6)
C6	0.0298 (9)	0.0261 (8)	0.0334 (10)	0.0017 (7)	0.0130 (8)	0.0010 (6)
C2	0.0357 (9)	0.0269 (8)	0.0256 (8)	−0.0006 (7)	0.0041 (7)	0.0001 (6)
C5	0.0360 (10)	0.0319 (9)	0.0264 (9)	0.0023 (7)	0.0019 (7)	−0.0006 (7)
C4	0.0448 (11)	0.0282 (9)	0.0337 (10)	0.0017 (8)	0.0114 (9)	−0.0033 (7)
C9	0.0296 (8)	0.0289 (8)	0.0252 (8)	0.0009 (7)	0.0015 (7)	−0.0023 (6)
C3	0.0317 (9)	0.0289 (8)	0.0360 (11)	−0.0002 (7)	0.0006 (8)	0.0058 (7)

Geometric parameters (Å, º) top

N2—C11	1.293 (2)	C8—C7	1.425 (2)
N2—C10	1.366 (2)	C11—H11	0.9300
N1—C11	1.379 (2)	C1—C5	1.384 (2)
N1—C7	1.415 (2)	C1—C2	1.386 (2)
N1—C6	1.4725 (19)	C1—C6	1.510 (2)
N3—C10	1.339 (2)	C6—H6A	0.9700
N3—N4	1.363 (2)	C6—H6B	0.9700
N3—H3N	0.897 (16)	C2—C3	1.385 (3)
N5—C3	1.325 (2)	C2—H2	0.9300
N5—C4	1.336 (2)	C5—C4	1.383 (2)
N4—C9	1.324 (2)	C5—H5	0.9300
O1—C7	1.231 (2)	C4—H4	0.9300
C8—C10	1.387 (2)	C9—H9	0.9300
C8—C9	1.418 (2)	C3—H3	0.9300

C11—N2—C10	112.37 (14)	C2—C1—C6	121.35 (15)
C11—N1—C7	123.10 (13)	N1—C6—C1	111.23 (11)
C11—N1—C6	117.67 (14)	N1—C6—H6A	109.4
C7—N1—C6	119.20 (13)	C1—C6—H6A	109.4
C10—N3—N4	111.39 (14)	N1—C6—H6B	109.4
C10—N3—H3N	126.6 (15)	C1—C6—H6B	109.4
N4—N3—H3N	122.0 (15)	H6A—C6—H6B	108.0
C3—N5—C4	117.08 (15)	C3—C2—C1	118.49 (16)
C9—N4—N3	105.96 (13)	C3—C2—H2	120.8
C10—C8—C9	104.34 (14)	C1—C2—H2	120.8
C10—C8—C7	119.42 (14)	C4—C5—C1	119.39 (16)
C9—C8—C7	136.22 (15)	C4—C5—H5	120.3
N2—C11—N1	126.12 (15)	C1—C5—H5	120.3
N2—C11—H11	116.9	N5—C4—C5	123.05 (16)
N1—C11—H11	116.9	N5—C4—H4	118.5
N3—C10—N2	125.17 (14)	C5—C4—H4	118.5
N3—C10—C8	107.61 (13)	N4—C9—C8	110.70 (15)
N2—C10—C8	127.23 (14)	N4—C9—H9	124.7
O1—C7—N1	120.18 (14)	C8—C9—H9	124.7
O1—C7—C8	128.22 (16)	N5—C3—C2	124.12 (17)
N1—C7—C8	111.59 (14)	N5—C3—H3	117.9
C5—C1—C2	117.87 (15)	C2—C3—H3	117.9
C5—C1—C6	120.77 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N5ⁱ	0.90 (2)	1.96 (2)	2.840 (2)	168 (2)
C4—H4···N4ⁱⁱ	0.93	2.61	3.526 (2)	167
C9—H9···N2ⁱⁱⁱ	0.93	2.36	3.289 (2)	174
C11—H11···O1^iv	0.93	2.52	3.430 (2)	167

Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) −x+1, y−1/2, −z; (iii) x−1, y, z−1; (iv) x+1, y, z+1.

Experimental details

Crystal data
Chemical formula	C₁₁H₉N₅O
M_r	227.23
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	296
a, b, c (Å)	4.6371 (3), 19.2731 (10), 5.8593 (3)
β (°)	102.498 (2)
V (Å³)	511.24 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.25 × 0.22 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	6285, 2603, 2201
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.680

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.085, 1.05
No. of reflections	2603
No. of parameters	158
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.16, −0.22

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N5ⁱ	0.90 (2)	1.96 (2)	2.840 (2)	168 (2)
C4—H4···N4ⁱⁱ	0.93	2.61	3.526 (2)	167
C9—H9···N2ⁱⁱⁱ	0.93	2.36	3.289 (2)	174
C11—H11···O1^iv	0.93	2.52	3.430 (2)	167

Symmetry codes: (i) −x+2, y+1/2, −z+1; (ii) −x+1, y−1/2, −z; (iii) x−1, y, z−1; (iv) x+1, y, z+1.

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UA TRS, CNRST) for the X-ray measurements.

References

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