organic compounds
d]pyrimidine-4(5H)-thione
of 1-ethylpyrazolo[3,4-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
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 = 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.
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
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Data collection: APEX2 (Bruker, 2009); cell 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
10.1107/S160053681401825X/hb7262sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681401825X/hb7262Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681401825X/hb7262Isup3.cml
(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.
The H atoms were located in a difference map and treated as riding with C—H = 0.93 Å (aromatic), C—H = 0.97 Å (methylene) and C—H = 0.96 Å, (methyl). All hydrogen with Uiso(H) = 1.2 Ueq (aromatic and methylene) and Uiso(H) = 1.5 Ueq for the methyl.
Data collection: APEX2 (Bruker, 2009); cell
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).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) |
C7H8N4S | V = 419.8 (5) Å3 |
Mr = 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)° |
Bruker X8 APEX CCD diffractometer | 1704 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1242 reflections with I > 2σ(I) |
Tmin = 0.578, Tmax = 0.746 | Rint = 0.059 |
4028 measured reflections |
R[F2 > 2σ(F2)] = 0.053 | H-atom parameters constrained |
wR(F2) = 0.139 | Δρmax = 0.29 e Å−3 |
S = 1.01 | Δρmin = −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 |
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 |
Symmetry codes: (i) −x, y+1/2, −z+1; (ii) x−1, y+1, z; (iii) x+1, y−1, z. |
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.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
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).