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

El Hafi, M.; Lahmidi, S.; Boulhaoua, M.; Ramli, Y.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314618004832

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 3| Part 3| March 2018| x180483

https://doi.org/10.1107/S2414314618004832

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

Mohamed El Hafi,^a ^* Sanae Lahmidi,^a Mohammed Boulhaoua,^a Youssef Ramli,^b El Mokhtar Essassi ^a and Joel T. Mague ^c

^aLaboratoire de Chimie Organique Hétérocyclique, Centre de Recherche Des Sciences des Médicaments, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bLaboratory of Medicinal Chemistry, Faculty of Medicine and Pharmacy, Mohammed V University Rabat, Morocco, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: m.elhafi1@yahoo.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 23 March 2018; accepted 25 March 2018; online 29 March 2018)

The title molecule, C₆H₆N₄O, is essentially planar [dihedral angle between the rings = 0.46 (9)°]. The crystal structure consists of sheets of molecules lying parallel to ( $[\overline{1}]$ 11) formed by a combination of N—H⋯O, C—H⋯O and C—H⋯H hydrogen bonds. The sheets are connected through π–π stacking interactions.

Keywords: crystal structure; pyrimidine; hydrogen bonds; π-stacking.

CCDC reference: 1832299

Structure description

As a continuation of our studies of pyrazolo[3,4-d]pyrimidine derivatives (El Fal et al., 2013 ; El Hafi et al., 2017 ), we now report the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
The title molecule with 50% probability ellipsoids.

The title molecule is essentially planar [dihedral angle between the pyrimidine and pyrazole rings = 0.46 (9)°]. In the crystal, centrosymmetric dimers are formed by pairwise N1—H1⋯O1ⁱ hydrogen bonds, which are connected into chains along the c-axis direction through pairwise C4—H4B⋯N4ⁱⁱⁱ hydrogen bonds. The chains are formed into sheets parallel to ( $[\overline{1}]$ 11) by C2—H2⋯O1ⁱⁱ hydrogen bonds (Table 1 and Fig. 2). The sheets are associated through π-stacking interactions between the bicyclic units with interplanar spacings of 3.3203 (5) Å (Fig. 3).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.95 (3)	1.84 (3)	2.7866 (18)	178 (2)
C2—H2⋯O1ⁱⁱ	0.99 (2)	2.46 (2)	3.399 (2)	157.8 (17)
C4—H4B⋯N4ⁱⁱⁱ	0.98 (3)	2.65 (3)	3.599 (2)	164 (2)
C5—H5⋯N2^iv	0.99 (2)	2.37 (2)	3.323 (2)	161.7 (18)
Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x+1, y+1, z; (iii) -x, -y+1, -z+1; (iv) x-1, y-1, z.

Figure 2
Detail of the hydrogen-bonding network viewed along the a-axis direction. N—H⋯O, C—H⋯O and C—H⋯N hydrogen bonds are shown, respectively, as blue, black and purple dashed lines.

Figure 3
Detail of the π-stacking interactions (dashed lines) leading to columns viewed along the b-axis direction

Synthesis and crystallization

A solution of 4-chloro-1-methyl-1H-pyrazolo[3,4-d]pyrimidine (0.3 g, 1.8 mmol) in (EtOH/H₂O, 8:2) was heated to reflux for 10 min. After cooling the solution at room temperature, the title compound in the form of colourless plates was obtained (yield: 80%; m.p. = 440–442 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₆H₆N₄O
M_r	150.15
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	150
a, b, c (Å)	3.8342 (2), 5.5701 (3), 15.0346 (9)
α, β, γ (°)	93.396 (4), 92.812 (4), 92.361 (4)
V (Å³)	319.83 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	0.96
Crystal size (mm)	0.21 × 0.07 × 0.01

Data collection
Diffractometer	Bruker D8 VENTURE PHOTON 100 CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.85, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	2352, 1191, 1037
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.618

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.108, 1.09
No. of reflections	1191
No. of parameters	124
H-atom treatment	All H-atom parameters refined
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.22
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2016 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1832299

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314618004832/hb4222sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314618004832/hb4222Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314618004832/hb4222Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314618004832/hb4222Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2016 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

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

Crystal data top

C₆H₆N₄O	Z = 2
M_r = 150.15	F(000) = 156
Triclinic, P1	D_x = 1.559 Mg m⁻³
a = 3.8342 (2) Å	Cu Kα radiation, λ = 1.54178 Å
b = 5.5701 (3) Å	Cell parameters from 1864 reflections
c = 15.0346 (9) Å	θ = 3.0–72.2°
α = 93.396 (4)°	µ = 0.96 mm⁻¹
β = 92.812 (4)°	T = 150 K
γ = 92.361 (4)°	Plate, colourless
V = 319.83 (3) Å³	0.21 × 0.07 × 0.01 mm

Data collection top

Bruker D8 VENTURE PHOTON 100 CMOS diffractometer	1191 independent reflections
Radiation source: INCOATEC IµS micro–focus source	1037 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.027
Detector resolution: 10.4167 pixels mm^-1	θ_max = 72.3°, θ_min = 3.0°
ω scans	h = −4→4
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −6→6
T_min = 0.85, T_max = 0.99	l = −18→18
2352 measured reflections

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)] = 0.042	Hydrogen site location: difference Fourier map
wR(F²) = 0.108	All H-atom parameters refined
S = 1.09	w = 1/[σ²(F_o²) + (0.0552P)² + 0.1016P] where P = (F_o² + 2F_c²)/3
1191 reflections	(Δ/σ)_max < 0.001
124 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
O1	0.2521 (3)	0.3096 (2)	0.91704 (8)	0.0260 (3)
N1	0.5472 (4)	0.6698 (3)	0.90191 (10)	0.0233 (4)
H1	0.614 (6)	0.673 (5)	0.9637 (19)	0.049 (7)*
N2	0.6103 (4)	0.8617 (2)	0.76659 (9)	0.0233 (4)
N3	0.3161 (4)	0.6313 (2)	0.64282 (9)	0.0215 (4)
N4	0.1240 (4)	0.4172 (3)	0.62663 (10)	0.0240 (4)
C1	0.3482 (4)	0.4668 (3)	0.86716 (10)	0.0208 (4)
C2	0.6662 (5)	0.8505 (3)	0.85226 (11)	0.0231 (4)
H2	0.810 (6)	0.977 (4)	0.8873 (15)	0.031 (5)*
C3	0.4137 (4)	0.6673 (3)	0.72991 (11)	0.0204 (4)
C4	0.4093 (5)	0.7771 (3)	0.57014 (12)	0.0270 (4)
H4A	0.443 (7)	0.942 (5)	0.5921 (18)	0.057 (8)*
H4B	0.232 (8)	0.747 (5)	0.5211 (19)	0.056 (8)*
H4C	0.623 (7)	0.724 (5)	0.5455 (19)	0.056 (7)*
C5	0.1014 (4)	0.3226 (3)	0.70515 (11)	0.0228 (4)
H5	−0.039 (6)	0.170 (4)	0.7095 (15)	0.034 (6)*
C6	0.2789 (4)	0.4723 (3)	0.77331 (11)	0.0208 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0359 (7)	0.0232 (6)	0.0192 (6)	−0.0038 (5)	0.0010 (5)	0.0067 (5)
N1	0.0301 (8)	0.0213 (7)	0.0185 (7)	−0.0009 (6)	−0.0005 (6)	0.0040 (6)
N2	0.0286 (8)	0.0194 (7)	0.0222 (7)	−0.0011 (6)	0.0011 (6)	0.0042 (6)
N3	0.0269 (8)	0.0208 (7)	0.0170 (7)	−0.0004 (5)	0.0022 (5)	0.0046 (5)
N4	0.0278 (8)	0.0215 (7)	0.0225 (7)	−0.0022 (6)	0.0009 (6)	0.0030 (6)
C1	0.0235 (9)	0.0197 (8)	0.0197 (8)	0.0021 (6)	0.0014 (6)	0.0037 (6)
C2	0.0272 (9)	0.0193 (8)	0.0229 (8)	0.0002 (7)	0.0009 (7)	0.0036 (7)
C3	0.0226 (8)	0.0201 (8)	0.0190 (8)	0.0022 (6)	0.0013 (6)	0.0045 (6)
C4	0.0329 (10)	0.0296 (10)	0.0194 (8)	−0.0015 (8)	0.0034 (7)	0.0083 (7)
C5	0.0259 (9)	0.0215 (8)	0.0210 (8)	−0.0007 (6)	0.0003 (6)	0.0046 (7)
C6	0.0232 (8)	0.0201 (8)	0.0199 (8)	0.0011 (6)	0.0020 (6)	0.0052 (6)

Geometric parameters (Å, º) top

O1—C1	1.242 (2)	N4—C5	1.326 (2)
N1—C2	1.365 (2)	C1—C6	1.425 (2)
N1—C1	1.398 (2)	C2—H2	0.99 (2)
N1—H1	0.95 (3)	C3—C6	1.394 (2)
N2—C2	1.301 (2)	C4—H4A	0.96 (3)
N2—C3	1.366 (2)	C4—H4B	0.98 (3)
N3—C3	1.345 (2)	C4—H4C	0.97 (3)
N3—N4	1.378 (2)	C5—C6	1.412 (2)
N3—C4	1.450 (2)	C5—H5	0.99 (2)

C2—N1—C1	124.42 (15)	N3—C3—C6	107.44 (15)
C2—N1—H1	119.3 (16)	N2—C3—C6	127.73 (16)
C1—N1—H1	116.2 (16)	N3—C4—H4A	109.3 (17)
C2—N2—C3	111.89 (15)	N3—C4—H4B	108.7 (17)
C3—N3—N4	110.92 (13)	H4A—C4—H4B	115 (2)
C3—N3—C4	128.07 (15)	N3—C4—H4C	110.3 (18)
N4—N3—C4	120.86 (14)	H4A—C4—H4C	109 (2)
C5—N4—N3	105.95 (14)	H4B—C4—H4C	104 (2)
O1—C1—N1	120.32 (15)	N4—C5—C6	110.88 (15)
O1—C1—C6	127.84 (15)	N4—C5—H5	119.6 (13)
N1—C1—C6	111.84 (14)	C6—C5—H5	129.5 (13)
N2—C2—N1	125.64 (16)	C3—C6—C5	104.80 (14)
N2—C2—H2	120.7 (13)	C3—C6—C1	118.47 (15)
N1—C2—H2	113.6 (13)	C5—C6—C1	136.72 (15)
N3—C3—N2	124.83 (15)

C3—N3—N4—C5	0.59 (19)	N3—N4—C5—C6	−0.25 (19)
C4—N3—N4—C5	176.43 (16)	N3—C3—C6—C5	0.51 (19)
C2—N1—C1—O1	179.52 (16)	N2—C3—C6—C5	−179.31 (16)
C2—N1—C1—C6	−0.9 (2)	N3—C3—C6—C1	179.64 (14)
C3—N2—C2—N1	−0.1 (3)	N2—C3—C6—C1	−0.2 (3)
C1—N1—C2—N2	0.7 (3)	N4—C5—C6—C3	−0.2 (2)
N4—N3—C3—N2	179.13 (15)	N4—C5—C6—C1	−179.04 (19)
C4—N3—C3—N2	3.7 (3)	O1—C1—C6—C3	−179.84 (16)
N4—N3—C3—C6	−0.70 (19)	N1—C1—C6—C3	0.7 (2)
C4—N3—C3—C6	−176.15 (16)	O1—C1—C6—C5	−1.1 (3)
C2—N2—C3—N3	−179.94 (16)	N1—C1—C6—C5	179.45 (19)
C2—N2—C3—C6	−0.1 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.95 (3)	1.84 (3)	2.7866 (18)	178 (2)
C2—H2···O1ⁱⁱ	0.99 (2)	2.46 (2)	3.399 (2)	157.8 (17)
C4—H4B···N4ⁱⁱⁱ	0.98 (3)	2.65 (3)	3.599 (2)	164 (2)
C5—H5···N2^iv	0.99 (2)	2.37 (2)	3.323 (2)	161.7 (18)

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

Acknowledgements

The support of NSF-MRI Grant #1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.

References

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