organic compounds
H-pyrazolo[3,4-d]pyrimidine
of 4-allylsulfanyl-1aLaboratoire 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, 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
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2.3. Refinement
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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: 1018090
10.1107/S1600536814018042/is5372sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536814018042/is5372Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536814018042/is5372Isup3.cml
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.
The allyl group is disordered over two sites with refined occupancies of 0.512 (6) and 0.488 (6). For the disordered group, tight distance restraints of S—C = 1.753 (2) Å, C—C = 1.453 (2) Å and C═C = 1.287 (2) Å, and constraint of same displacement parameters were applied. 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 N—H = 0.86 Å (N–H), and with Uiso(H) = 1.2Ueq(C,N).
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).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 |
C8H8N4S | V = 1837.0 (11) Å3 |
Mr = 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 |
Bruker X8 APEX diffractometer | 2189 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2009) | 1093 reflections with I > 2σ(I) |
Tmin = 0.641, Tmax = 0.746 | Rint = 0.068 |
20928 measured reflections |
R[F2 > 2σ(F2)] = 0.056 | 6 restraints |
wR(F2) = 0.181 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.28 e Å−3 |
2189 reflections | Δρmin = −0.31 e Å−3 |
128 parameters |
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 |
Symmetry code: (i) −x+1, −y+2, −z+2. |
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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