Crystal structure of 4-allyl­sulfanyl-1H-pyrazolo­[3,4-d]pyrimidine

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

doi:10.1107/S1600536814018042

organic compounds

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ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o1038

doi:10.1107/S1600536814018042

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Crystal structure of 4-allylsulfanyl-1H-pyrazolo[3,4-d]pyrimidine

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 H. Ishida, Okayama University, Japan (Received 27 July 2014; accepted 6 August 2014; online 23 August 2014)

In the title compound, C₈H₈N₄S, the pyrazolo[3,4-d]pyrimidine ring system is essentially planar, with a maximum deviation from the mean plane of 0.025 (3) Å. The allyl group is disordered over two sites in a 0.512 (6):0.488 (6) ratio. In the crystal, molecules are linked by pairs of N—H⋯N hydrogen bonds, forming inversion dimers with an R₂²(8) graph-set motif.

Keywords: crystal structure; pyrazolopyrimidine; thiopyrazolopyrimidine; disorder.

CCDC reference: 1018090

1. Related literature

Antiviral, antimycobacterial and anticancer properties of pyrazolo[3,4-d]pyrimidine-4(5H)-thione derivatives are described, respectively, by Yuan et al. (2013 ), Ballell et al. (2007 ) and Rashad et al. (2011 ), and Alsubari et al. (2011 ). A similar structure, namely 4-benzylsulfanyl-1H-pyrazolo[3,4-d]pyrimidine, is reported by El Fal et al. (2013 ).

2. Experimental

2.1. Crystal data

C₈H₈N₄S
M_r = 192.24
Orthorhombic, P b c n
a = 18.537 (6) Å
b = 5.1997 (17) Å
c = 19.059 (7) Å
V = 1837.0 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 296 K
0.39 × 0.34 × 0.29 mm

2.2. Data collection

Bruker X8 APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.641, T_max = 0.746
20928 measured reflections
2189 independent reflections
1093 reflections with I > 2σ(I)
R_int = 0.068

2.3. Refinement

R[F² > 2σ(F²)] = 0.056
wR(F²) = 0.181
S = 1.02
2189 reflections
128 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3N⋯N2ⁱ	0.86	2.09	2.940 (4)	172
Symmetry code: (i) -x+1, -y+2, -z+2.

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: 1018090

Crystal structure: contains datablock I. DOI: 10.1107/S1600536814018042/is5372sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814018042/is5372Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814018042/is5372Isup3.cml

checkCIF report

Related literature top

Antiviral, antimycobacterial and anticancer properties of pyrazolo[3,4-d]pyrimidine-4(5H)-thione derivatives are described, respectively, by Yuan et al. (2013), Ballell et al. (2007) and Rashad et al. (2011), and Alsubari et al. (2011). A similar structure, namely 4-benzylsulfanyl-1H-pyrazolo[3,4-d]pyrimidine, is reported by El Fal et al. (2013).

Experimental top

1H,5H-pyrazolo[3,4-d]pyrimidine-4-thione (0.5 g, 3.29 mmol), allyl bromide (0.5 ml, 5.70 mmol) and potassium carbonate (0.64 g, 4.8 mmol) with a catalytic amount of tetra-n-butylammonium bromide were stirred in DMF (15 ml) for 72 h. The solid obtained was removed by filtration and the solvent evaporated under vacuum. The solid product was purified by recrystallization from ethanol to afford yellow crystals in 55% yield.

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 the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles.
	Fig. 2. Packing diagram of the title compound viewed along the b axis, showing molecules linked through N3–H3N···N2 hydrogen bond (dashed lines).

4-Allylsulfanyl-1H-pyrazolo[3,4-d]pyrimidine top

Crystal data top

C₈H₈N₄S	F(000) = 800
M_r = 192.24	D_x = 1.390 Mg m⁻³
Orthorhombic, Pbcn	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -p 2n 2ab	Cell parameters from 2189 reflections
a = 18.537 (6) Å	θ = 2.4–27.9°
b = 5.1997 (17) Å	µ = 0.31 mm⁻¹
c = 19.059 (7) Å	T = 296 K
V = 1837.0 (11) Å³	Block, yellow
Z = 8	0.39 × 0.34 × 0.29 mm

Data collection top

Bruker X8 APEX diffractometer	2189 independent reflections
Radiation source: fine-focus sealed tube	1093 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.068
ϕ and ω scans	θ_max = 27.9°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −15→24
T_min = 0.641, T_max = 0.746	k = −6→6
20928 measured reflections	l = −24→24

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)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.181	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0784P)² + 0.5307P] where P = (F_o² + 2F_c²)/3
2189 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.28 e Å⁻³
6 restraints	Δρ_min = −0.31 e Å⁻³

Crystal data top

C₈H₈N₄S	V = 1837.0 (11) Å³
M_r = 192.24	Z = 8
Orthorhombic, Pbcn	Mo Kα radiation
a = 18.537 (6) Å	µ = 0.31 mm⁻¹
b = 5.1997 (17) Å	T = 296 K
c = 19.059 (7) Å	0.39 × 0.34 × 0.29 mm

Data collection top

Bruker X8 APEX diffractometer	2189 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1093 reflections with I > 2σ(I)
T_min = 0.641, T_max = 0.746	R_int = 0.068
20928 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	6 restraints
wR(F²) = 0.181	H-atom parameters constrained
S = 1.02	Δρ_max = 0.28 e Å⁻³
2189 reflections	Δρ_min = −0.31 e Å⁻³
128 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	Occ. (<1)
S1	0.66313 (5)	0.15662 (17)	0.85306 (5)	0.0890 (4)
N1	0.53488 (15)	0.3882 (5)	0.85359 (15)	0.0819 (8)
N2	0.49883 (12)	0.7352 (5)	0.92947 (15)	0.0759 (8)
N3	0.58954 (12)	0.8446 (5)	1.01342 (15)	0.0760 (8)
H3N	0.5667	0.9680	1.0337	0.091*
N4	0.65714 (13)	0.7630 (6)	1.03189 (17)	0.0867 (9)
C1	0.48931 (17)	0.5665 (7)	0.8781 (2)	0.0887 (10)
H1	0.4446	0.5730	0.8561	0.106*
C2	0.56370 (15)	0.7078 (5)	0.96002 (17)	0.0639 (8)
C3	0.67252 (15)	0.5738 (7)	0.98923 (19)	0.0787 (9)
H3	0.7154	0.4812	0.9902	0.094*
C4	0.61592 (14)	0.5282 (5)	0.94180 (17)	0.0654 (8)
C5	0.59890 (15)	0.3712 (5)	0.88464 (18)	0.0710 (9)
C6A	0.6154 (5)	−0.011 (2)	0.7877 (4)	0.1188 (19)	0.512 (6)
H6A1	0.6140	−0.1915	0.7999	0.143*	0.512 (6)
H6A2	0.5660	0.0515	0.7869	0.143*	0.512 (6)
C7A	0.6458 (4)	0.0154 (16)	0.7178 (5)	0.0919 (15)	0.512 (6)
H7A	0.6385	0.1722	0.6954	0.110*	0.512 (6)
C8A	0.682 (3)	−0.155 (6)	0.6835 (9)	0.121 (3)	0.512 (6)
H8A1	0.6906	−0.3151	0.7035	0.145*	0.512 (6)
H8A2	0.6989	−0.1179	0.6388	0.145*	0.512 (6)
C6B	0.6188 (5)	0.019 (2)	0.7806 (4)	0.1188 (19)	0.488 (6)
H6B1	0.5749	−0.0628	0.7973	0.143*	0.488 (6)
H6B2	0.6046	0.1563	0.7491	0.143*	0.488 (6)
C7B	0.6598 (4)	−0.1692 (16)	0.7409 (5)	0.0919 (15)	0.488 (6)
H7B	0.6757	−0.3111	0.7663	0.110*	0.488 (6)
C8B	0.677 (3)	−0.168 (7)	0.6756 (10)	0.121 (3)	0.488 (6)
H8B1	0.6634	−0.0313	0.6470	0.145*	0.488 (6)
H8B2	0.7042	−0.3024	0.6569	0.145*	0.488 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0830 (6)	0.0671 (6)	0.1169 (9)	0.0018 (4)	0.0180 (5)	−0.0160 (5)
N1	0.0756 (16)	0.0624 (16)	0.108 (2)	−0.0024 (13)	−0.0034 (15)	−0.0048 (15)
N2	0.0599 (14)	0.0576 (15)	0.110 (2)	0.0017 (11)	−0.0054 (14)	−0.0014 (16)
N3	0.0589 (13)	0.0613 (15)	0.108 (2)	0.0089 (11)	0.0049 (14)	−0.0078 (15)
N4	0.0621 (15)	0.083 (2)	0.115 (2)	0.0106 (13)	−0.0057 (14)	−0.0153 (18)
C1	0.0683 (18)	0.073 (2)	0.124 (3)	−0.0002 (17)	−0.0086 (19)	0.000 (2)
C2	0.0604 (15)	0.0472 (15)	0.084 (2)	−0.0016 (12)	0.0065 (15)	0.0029 (15)
C3	0.0630 (17)	0.069 (2)	0.104 (3)	0.0116 (14)	0.0028 (17)	−0.009 (2)
C4	0.0584 (15)	0.0511 (16)	0.087 (2)	−0.0005 (12)	0.0069 (15)	0.0023 (16)
C5	0.0704 (18)	0.0502 (17)	0.092 (2)	−0.0041 (14)	0.0122 (17)	0.0058 (17)
C6A	0.103 (3)	0.098 (4)	0.155 (4)	−0.023 (3)	0.038 (3)	−0.054 (3)
C7A	0.094 (3)	0.076 (4)	0.106 (4)	−0.009 (3)	−0.019 (3)	0.018 (3)
C8A	0.102 (6)	0.167 (5)	0.093 (5)	−0.012 (4)	−0.007 (6)	−0.010 (5)
C6B	0.103 (3)	0.098 (4)	0.155 (4)	−0.023 (3)	0.038 (3)	−0.054 (3)
C7B	0.094 (3)	0.076 (4)	0.106 (4)	−0.009 (3)	−0.019 (3)	0.018 (3)
C8B	0.102 (6)	0.167 (5)	0.093 (5)	−0.012 (4)	−0.007 (6)	−0.010 (5)

Geometric parameters (Å, º) top

S1—C5	1.739 (3)	C4—C5	1.397 (4)
S1—C6A	1.759 (2)	C6A—C7A	1.452 (2)
S1—C6B	1.759 (2)	C6A—H6A1	0.9700
N1—C5	1.329 (4)	C6A—H6A2	0.9700
N1—C1	1.339 (4)	C7A—C8A	1.287 (2)
N2—C1	1.326 (4)	C7A—H7A	0.9300
N2—C2	1.344 (4)	C8A—H8A1	0.9300
N3—C2	1.331 (4)	C8A—H8A2	0.9300
N3—N4	1.369 (3)	C6B—C7B	1.453 (2)
N3—H3N	0.8600	C6B—H6B1	0.9700
N4—C3	1.308 (4)	C6B—H6B2	0.9700
C1—H1	0.9300	C7B—C8B	1.287 (2)
C2—C4	1.389 (4)	C7B—H7B	0.9300
C3—C4	1.405 (4)	C8B—H8B1	0.9300
C3—H3	0.9300	C8B—H8B2	0.9300

C5—S1—C6A	102.6 (4)	C7A—C6A—H6A1	108.7
C5—S1—C6B	102.3 (4)	S1—C6A—H6A1	108.7
C5—N1—C1	117.0 (3)	C7A—C6A—H6A2	108.7
C1—N2—C2	111.6 (3)	S1—C6A—H6A2	108.7
C2—N3—N4	111.1 (3)	H6A1—C6A—H6A2	107.6
C2—N3—H3N	124.4	C8A—C7A—C6A	127.1 (11)
N4—N3—H3N	124.4	C8A—C7A—H7A	116.5
C3—N4—N3	105.8 (3)	C6A—C7A—H7A	116.5
N2—C1—N1	129.2 (3)	C7A—C8A—H8A1	120.0
N2—C1—H1	115.4	C7A—C8A—H8A2	120.0
N1—C1—H1	115.4	H8A1—C8A—H8A2	120.0
N3—C2—N2	126.7 (3)	C7B—C6B—S1	116.0 (7)
N3—C2—C4	107.4 (3)	C7B—C6B—H6B1	108.3
N2—C2—C4	125.9 (3)	S1—C6B—H6B1	108.3
N4—C3—C4	111.4 (3)	C7B—C6B—H6B2	108.3
N4—C3—H3	124.3	S1—C6B—H6B2	108.3
C4—C3—H3	124.3	H6B1—C6B—H6B2	107.4
C2—C4—C5	115.5 (3)	C8B—C7B—C6B	129.2 (10)
C2—C4—C3	104.2 (3)	C8B—C7B—H7B	115.4
C5—C4—C3	140.2 (3)	C6B—C7B—H7B	115.4
N1—C5—C4	120.7 (3)	C7B—C8B—H8B1	120.0
N1—C5—S1	120.0 (3)	C7B—C8B—H8B2	120.0
C4—C5—S1	119.3 (2)	H8B1—C8B—H8B2	120.0
C7A—C6A—S1	114.1 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N2ⁱ	0.86	2.09	2.940 (4)	172

Symmetry code: (i) −x+1, −y+2, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3N···N2ⁱ	0.86	2.09	2.940 (4)	172

Symmetry code: (i) −x+1, −y+2, −z+2.

Acknowledgements

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

References

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