Crystal structure of 4-allyl-sulfanyl-1H-pyrazolo-[3,4-d]pyrimidine.

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, mol-ecules are linked by pairs of N-H⋯N hydrogen bonds, forming inversion dimers with an R 2 (2)(8) graph-set motif.

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 ▶).

Experimental

Crystal data

C8H8N4S

M = 192.24

Orthorhombic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.056

wR(F 2) = 0.181

S = 1.02

2189 reflections

128 parameters

6 restraints

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.31 e Å−3

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 ▶).

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

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

Click here for additional data file.

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

Click here for additional data file.

. DOI: 10.1107/S1600536814018042/is5372fig1.tif

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.

Click here for additional data file.

b N . DOI: 10.1107/S1600536814018042/is5372fig2.tif

Packing diagram of the title compound viewed along the b axis, showing mol­ecules linked through N3–H3N⋯N2 hydrogen bond (dashed lines).

CCDC reference: 1018090

Additional supporting information: crystallographic information; 3D view; checkCIF report

C8H8N4S	F(000) = 800
Mr = 192.24	Dx = 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

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

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(Fo2) + (0.0784P)2 + 0.5307P] where P = (Fo2 + 2Fc2)/3
2189 reflections	(Δ/σ)max < 0.001
128 parameters	Δρmax = 0.28 e Å−3
6 restraints	Δρmin = −0.31 e Å−3

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.

	x	y	z	Uiso*/Ueq	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)

	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)

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)

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

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) .