Crystal structure of 1-ethyl­pyrazolo[3,4-d]pyrimidine-4(5H)-thione

El Fal, M.; Ramli, Y.; Essassi, E.M.; Saadi, M.; El Ammari, L.

doi:10.1107/S160053681401825X

organic compounds

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ISSN: 2056-9890

Volume 70| Part 9| September 2014| Pages o1005-o1006

doi:10.1107/S160053681401825X

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Crystal structure of 1-ethylpyrazolo[3,4-d]pyrimidine-4(5H)-thione

Mohammed El Fal,^a ^* Youssef Ramli,^b El Mokhtar Essassi,^a Mohamed Saadi ^c and Lahcen El Ammari ^c

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V-Agdal, Rabat, Morocco, ^bLaboratoire National de Contrôle des Médicaments, D M P, Ministère de la Santé, Madinat Al Irnane, BP 6206, Rabat, Morocco, and ^cLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: elfal_mohammed@yahoo.fr

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 29 July 2014; accepted 9 August 2014; online 16 August 2014)

In the title compound, C₇H₈N₄S, the methyl C atom is displaced by 1.232 (7) Å from the mean plane of the pyrazolo[3,4-d]pyrimidine ring system (r.m.s. deviation = 0.007 Å). The N—N—C—C_m (m = methyl) torsion angle is −60.3 (6)°. In the crystal, molecules are linked by N—H⋯S hydrogen bonds, generating [010] chains, which are reinforced by C—H⋯N interactions. The chains are cross-linked by weak C—H⋯S hydrogen bonds, generating (001) sheets.

Keywords: crystal structure; pyrazolo[3,4-d]pyrimidine; biological activity; hydrogen bonding.

CCDC reference: 1018657

1. Related literature

For the biological activity of pyrazolo[3,4-d]pyrimidine derivatives, see: Rashad et al. (2008 , 2011 ); Ballell et al. (2007 ). For related structures, see: El Fal et al. (2013 ); Radi et al. (2013 ); Alsubari et al. (2011 ).

2. Experimental

2.1. Crystal data

C₇H₈N₄S
M_r = 180.23
Monoclinic, P 2₁
a = 4.472 (4) Å
b = 5.353 (4) Å
c = 17.573 (12) Å
β = 93.71 (4)°
V = 419.8 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 296 K
0.38 × 0.34 × 0.29 mm

2.2. Data collection

Bruker X8 APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.578, T_max = 0.746
4028 measured reflections
1704 independent reflections
1242 reflections with I > 2σ(I)
R_int = 0.059

2.3. Refinement

R[F² > 2σ(F²)] = 0.053
wR(F²) = 0.139
S = 1.01
1704 reflections
109 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack & Bernardinelli (2000 ), 652 Friedel pairs
Absolute structure parameter: −0.11 (16)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1ⁱ	0.89	2.48	3.333 (4)	161
C5—H5⋯S1ⁱⁱ	0.93	2.75	3.685 (5)	179
C3—H3⋯N2ⁱⁱⁱ	0.93	2.60	3.528 (6)	174
Symmetry codes: (i) $[-x, y+{\script{1\over 2}}, -z+1]$ ; (ii) x-1, y+1, z; (iii) x+1, y-1, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus; 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: PLATON (Spek, 2009 ) and publCIF (Westrip, 2010 ).

Supporting information

CCDC reference: 1018657

Crystal structure: contains datablock I. DOI: 10.1107/S160053681401825X/hb7262sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681401825X/hb7262Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681401825X/hb7262Isup3.cml

checkCIF report

Comment top

Pyrazolo [3,4-d] pyrimidine derivatives have attracted considerable attention from researchers due to their bioactive and pharmaceutical properties. Many members of this family are widely used as antiviral (Rashad et al., 2008); anti-mycobacterial (Ballell et al. 2007) and anticancer agents (Rashad et al. 2011). The present paper is a continuation of our research work devoted to the development of pyrazolo [3,4-d] pyrimidine derivatives with potential pharmacological activities (El Fal et al., 2013; Radi et al., 2013; Alsubari et al., 2011).

The molecule of the title compound is build up from two fused five- and six-membered heterocycles linked to an ethyl group and to S atom as shown in Fig.1. The pyrazolo[3,4-d]pyrimidine ring is nearly perpendicular to the ethyl group as indicated by the torsion angle C7C6N3N4 of -60.3 (6)°.

In the crystal, the molecules are linked together by a weak intermolecular N1–H1···S1, C5–H5···S1 and C3–H3···N2 interactions, in the way to build a two-dimensional network (see Fig.2 and Table 1).

Related literature top

For the biological activity of pyrazolo[3,4-d]pyrimidine derivatives, see: Rashad et al. (2008, 2011); Ballell et al. (2007). For related structures, see: El Fal et al. (2013); Radi et al. (2013); Alsubari et al. (2011).

Experimental top

(0,54 g, 3.04 mmol) of 1-ethyl-pyrazolo [3, 4 - d] pyrimidin-4 (5H)-one and (0,84 g, 3.65 mmol) of phosphorus pentasulfide were refluxed in pyridine for 4 h. Then the solvent is evaporated under reduced pressure; the precipitate formed is washed with hot water and recrystallized from ethanol solution to afford the title compound as yellow blocks.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT-Plus (Bruker, 2009); data reduction: SAINT-Plus (Bruker, 2009); 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: PLATON (Spek, 2009) and publCIF (Westrip, 2010).

Figures top

	Fig. 1. Molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.
	Fig. 2. Structure projection along (0 1 1) of the title compound, showing molecules linked through hydrogen bonds (dashed lines).

1-Ethylpyrazolo[3,4-d]pyrimidine-4(5H)-thione top

Crystal data top

C₇H₈N₄S	F(000) = 188
M_r = 180.23	D_x = 1.426 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2yb	Cell parameters from 1704 reflections
a = 4.472 (4) Å	θ = 3.5–27.5°
b = 5.353 (4) Å	µ = 0.33 mm⁻¹
c = 17.573 (12) Å	T = 296 K
β = 93.71 (4)°	Block, yellow
V = 419.8 (5) Å³	0.38 × 0.34 × 0.29 mm
Z = 2

Data collection top

Bruker X8 APEX CCD diffractometer	1704 independent reflections
Radiation source: fine-focus sealed tube	1242 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 27.5°, θ_min = 3.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −5→5
T_min = 0.578, T_max = 0.746	k = −6→5
4028 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.139	w = 1/[σ²(F_o²) + (0.P)²] where P = (F_o² + 2F_c²)/3
S = 1.01	(Δ/σ)_max < 0.001
1704 reflections	Δρ_max = 0.29 e Å⁻³
109 parameters	Δρ_min = −0.36 e Å⁻³
1 restraint	Absolute structure: Flack & Bernardinelli (2000), 652 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.11 (16)

Crystal data top

C₇H₈N₄S	V = 419.8 (5) Å³
M_r = 180.23	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 4.472 (4) Å	µ = 0.33 mm⁻¹
b = 5.353 (4) Å	T = 296 K
c = 17.573 (12) Å	0.38 × 0.34 × 0.29 mm
β = 93.71 (4)°

Data collection top

Bruker X8 APEX CCD diffractometer	1704 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1242 reflections with I > 2σ(I)
T_min = 0.578, T_max = 0.746	R_int = 0.059
4028 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.053	H-atom parameters constrained
wR(F²) = 0.139	Δρ_max = 0.29 e Å⁻³
S = 1.01	Δρ_min = −0.36 e Å⁻³
1704 reflections	Absolute structure: Flack & Bernardinelli (2000), 652 Friedel pairs
109 parameters	Absolute structure parameter: −0.11 (16)
1 restraint

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	0.2656 (8)	0.2169 (7)	0.6200 (2)	0.0340 (9)
C2	0.3666 (8)	0.2465 (8)	0.6972 (2)	0.0349 (9)
C3	0.5729 (9)	0.1222 (9)	0.7490 (2)	0.0421 (10)
H3	0.6856	−0.0166	0.7370	0.050*
C4	0.2506 (9)	0.4396 (7)	0.7391 (2)	0.0386 (10)
C5	−0.0448 (9)	0.5752 (8)	0.6444 (2)	0.0438 (11)
H5	−0.1874	0.6853	0.6230	0.053*
C6	0.3360 (13)	0.5872 (10)	0.8749 (3)	0.0669 (16)
H6A	0.1925	0.7165	0.8595	0.080*
H6B	0.5229	0.6675	0.8919	0.080*
C7	0.2207 (15)	0.4383 (15)	0.9390 (3)	0.091 (3)
H7A	0.1876	0.5471	0.9810	0.137*
H7B	0.3652	0.3131	0.9550	0.137*
H7C	0.0355	0.3592	0.9221	0.137*
N1	0.0543 (7)	0.3928 (6)	0.59849 (19)	0.0407 (9)
H1	−0.0256	0.4046	0.5509	0.049*
N2	0.0419 (8)	0.6091 (7)	0.71546 (19)	0.0435 (9)
N3	0.3849 (9)	0.4260 (7)	0.80986 (17)	0.0482 (10)
N4	0.5830 (8)	0.2300 (8)	0.81616 (19)	0.0513 (10)
S1	0.3799 (2)	0.0022 (2)	0.55937 (5)	0.0413 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0340 (18)	0.030 (2)	0.038 (2)	−0.0022 (18)	0.0034 (16)	0.0046 (17)
C2	0.0340 (18)	0.030 (2)	0.040 (2)	−0.0013 (19)	0.0000 (15)	0.0005 (18)
C3	0.046 (2)	0.039 (2)	0.040 (2)	0.011 (2)	−0.0064 (17)	0.0030 (19)
C4	0.041 (2)	0.036 (3)	0.038 (2)	−0.0003 (19)	0.0021 (16)	−0.0011 (17)
C5	0.036 (2)	0.038 (3)	0.056 (3)	0.0102 (19)	−0.0030 (18)	0.005 (2)
C6	0.089 (4)	0.067 (4)	0.045 (3)	0.002 (3)	0.005 (2)	−0.017 (2)
C7	0.094 (4)	0.128 (8)	0.053 (3)	−0.003 (5)	0.016 (3)	−0.009 (3)
N1	0.0406 (18)	0.037 (2)	0.0440 (19)	0.0066 (17)	−0.0044 (15)	0.0078 (16)
N2	0.050 (2)	0.034 (2)	0.046 (2)	0.0076 (18)	0.0027 (16)	−0.0015 (16)
N3	0.059 (2)	0.052 (3)	0.0337 (17)	0.0086 (19)	0.0001 (15)	−0.0048 (16)
N4	0.051 (2)	0.058 (3)	0.044 (2)	0.015 (2)	−0.0072 (16)	−0.0002 (18)
S1	0.0449 (5)	0.0390 (6)	0.0388 (5)	0.0052 (6)	−0.0053 (4)	−0.0052 (5)

Geometric parameters (Å, º) top

C1—N1	1.370 (5)	C5—H5	0.9300
C1—C2	1.410 (5)	C6—N3	1.459 (5)
C1—S1	1.669 (4)	C6—C7	1.499 (7)
C2—C4	1.390 (5)	C6—H6A	0.9700
C2—C3	1.419 (6)	C6—H6B	0.9700
C3—N4	1.312 (5)	C7—H7A	0.9600
C3—H3	0.9300	C7—H7B	0.9600
C4—N3	1.347 (5)	C7—H7C	0.9600
C4—N2	1.348 (5)	N1—H1	0.8900
C5—N2	1.296 (5)	N3—N4	1.373 (5)
C5—N1	1.359 (5)

N1—C1—C2	111.1 (3)	N3—C6—H6B	109.5
N1—C1—S1	122.1 (3)	C7—C6—H6B	109.5
C2—C1—S1	126.8 (3)	H6A—C6—H6B	108.1
C4—C2—C1	119.1 (4)	C6—C7—H7A	109.5
C4—C2—C3	104.9 (3)	C6—C7—H7B	109.5
C1—C2—C3	136.0 (4)	H7A—C7—H7B	109.5
N4—C3—C2	110.8 (4)	C6—C7—H7C	109.5
N4—C3—H3	124.6	H7A—C7—H7C	109.5
C2—C3—H3	124.6	H7B—C7—H7C	109.5
N3—C4—N2	125.4 (4)	C5—N1—C1	125.2 (3)
N3—C4—C2	106.9 (4)	C5—N1—H1	112.4
N2—C4—C2	127.7 (3)	C1—N1—H1	122.4
N2—C5—N1	125.7 (4)	C5—N2—C4	111.2 (3)
N2—C5—H5	117.1	C4—N3—N4	111.2 (3)
N1—C5—H5	117.1	C4—N3—C6	127.6 (4)
N3—C6—C7	110.5 (5)	N4—N3—C6	121.2 (4)
N3—C6—H6A	109.5	C3—N4—N3	106.2 (3)
C7—C6—H6A	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.89	2.48	3.333 (4)	161
C5—H5···S1ⁱⁱ	0.93	2.75	3.685 (5)	179
C3—H3···N2ⁱⁱⁱ	0.93	2.60	3.528 (6)	174

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1ⁱ	0.89	2.48	3.333 (4)	161
C5—H5···S1ⁱⁱ	0.93	2.75	3.685 (5)	179
C3—H3···N2ⁱⁱⁱ	0.93	2.60	3.528 (6)	174

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

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the University Mohammed V-Agdal, Rabat, Morocco, for financial support.

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