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

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-Cm (m = meth-yl) torsion angle is -60.3 (6)°. In the crystal, mol-ecules are linked by N-H⋯S hydrogen bonds, generating [010] chains, which are reinforced by C-H⋯N inter-actions. The chains are cross-linked by weak C-H⋯S hydrogen bonds, generating (001) sheets.

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 ▶).

Experimental

Crystal data

C7H8N4S

M = 180.23

Monoclinic,

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

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

Refinement

R[F 2 > 2σ(F 2)] = 0.053

wR(F 2) = 0.139

S = 1.01

1704 reflections

109 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.36 e Å−3

Absolute structure: Flack & Bernardinelli (2000 ▶), 652 Friedel pairs

Absolute structure parameter: −0.11 (16)

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/S160053681401825X/hb7262sup1.cif

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

Click here for additional data file.

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

Click here for additional data file.

. DOI: 10.1107/S160053681401825X/hb7262fig1.tif

Mol­ecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Click here for additional data file.

. DOI: 10.1107/S160053681401825X/hb7262fig2.tif

Structure projection along (0 1 1) of the title compound, showing mol­ecules linked through hydrogen bonds (dashed lines).

CCDC reference: 1018657

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

C7H8N4S	F(000) = 188
Mr = 180.23	Dx = 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

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

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(Fo2) + (0.P)2] where P = (Fo2 + 2Fc2)/3
S = 1.01	(Δ/σ)max < 0.001
1704 reflections	Δρmax = 0.29 e Å−3
109 parameters	Δρmin = −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)

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
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)

	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)

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

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

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) ; (ii) ; (iii) .