organic compounds
4-(Prop-2-yn-1-ylsulfanyl)-1H-pyrazolo[3,4-d]pyrimidine
aLaboratoire de Chimie Organique Hétérocyclique, Centre de Recherche Des Sciences des Médicaments, Pôle de Compétence Pharmacochimie, Av Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, bLaboratory of Medicinal Chemistry, Faculty of Medicine and Pharmacy, Mohammed V University, Rabat, Morocco, and cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
*Correspondence e-mail: elhafi.mohamed1@gmail.com
The 8H6N4S, consists of two independent molecules differing in the orientation of the side chain. In the crystal, molecules form dimers through N—H⋯N hydrogen bonds. The dimers stack along the a-axis direction with weak π–π stacking interactions [centroid–centroid distances of 3.898 (2) and 3.908 (2) Å]. The crystal studied was refined as a two-component twin.
of the title compound, CKeywords: crystal structure; hydrogen bond; π-stacking; pyrimidine.
CCDC reference: 1581006
Structure description
As a continuation of our research work devoted to the development of S-substituted pyrazolo[3,4-d]pyrimidine derivatives (El Fal et al., 2014), we have studied the action of propargyl bromide towards 1H-pyrazolo[3,4-d]pyrimidine-4(5H)-thione, using ethanol as solvent and potassium hydroxide as base. The title compound was isolated and its structure was established.
The ). Thus, the dihedral angle between the mean plane of the N1–N4/C1–C5 unit and that defined by S1/C6–C8 is 79.3 (2)°, while the corresponding angle in the second molecule is 76.4 (2)°. The bicyclic cores are planar with the maximum deviation from the mean plane being 0.016 (3) Å (C5) in the first molecule (r.m.s. deviation = 0.0094 Å) and −0.015 (3) Å (C13) in the second (r.m.s. deviation = 0.0086 Å). The dihedral angle between the bicyclic units is 76.42 (7)°.
of the title compound consists of two independent molecules differing to a small extent in the orientation of the side chain with respect to the bicyclic core (Fig. 1In the crystal, each independent molecule forms a dimer with an inversion-related counterpart through pairwise N—H⋯N hydrogen bonds (Table 1). The dimers stack along the a-axis direction with the aid of head-to-tail π–π-stacking interactions (Fig. 2). For the molecules containing S1, the centroid–centroid distance is 3.898 (2) Å, while for those containing S2, the distance is 3.908 (2) Å. In both instances, the dihedral angle between the associated planes is 1.2 (2)°.
Synthesis and crystallization
To a solution of 1H-pyrazolo[3,4-d]pyrimidine-4-thione (0.5 g, 3.3 mmol) in EtOH (15 ml) was added propargyl bromide (0.25 ml, 3.3 mmol) and potassium hydroxide (0.19 g, 3.3 mmol). The mixture was refluxed for 8 h, and after cooling, the reaction mixture was poured slowly into an ice bath under stirring to homogenize the whole. The solid product was precipitated and filtered. The residue was purified by recrystallization from ethanol to afford the title compound as colourless crystals (65% yield; m.p. 398–400 K).
Refinement
Crystal data, data collection and structure . The studied crystal was found to be twinned by a 180° rotation about the b* axis, and the model was refined as a two-component twin using CELL_NOW (Sheldrick, 2008b).
details are summarize in Table 2Structural data
CCDC reference: 1581006
https://doi.org/10.1107/S2414314617015267/bh4028sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617015267/bh4028Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617015267/bh4028Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314617015267/bh4028Isup4.cml
Data collection: APEX3 (Bruker, 2016); cell
SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008a).C8H6N4S | F(000) = 392 |
Mr = 190.23 | Dx = 1.528 Mg m−3 |
Triclinic, P1 | Melting point: 398 K |
a = 4.8851 (1) Å | Cu Kα radiation, λ = 1.54178 Å |
b = 9.8472 (3) Å | Cell parameters from 7441 reflections |
c = 17.4428 (5) Å | θ = 5.1–72.4° |
α = 86.380 (1)° | µ = 3.09 mm−1 |
β = 89.606 (1)° | T = 150 K |
γ = 81.027 (1)° | Plate, colourless |
V = 827.15 (4) Å3 | 0.29 × 0.09 × 0.03 mm |
Z = 4 |
Bruker D8 VENTURE PHOTON 100 CMOS diffractometer | 11079 independent reflections |
Radiation source: INCOATEC IµS micro-focus source | 9249 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.039 |
Detector resolution: 10.4167 pixels mm-1 | θmax = 72.4°, θmin = 2.5° |
ω scans | h = −6→6 |
Absorption correction: multi-scan (TWINABS; Sheldrick, 2009) | k = −12→11 |
Tmin = 0.46, Tmax = 0.91 | l = −21→21 |
11085 measured reflections |
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)] = 0.059 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.163 | All H-atom parameters refined |
S = 1.09 | w = 1/[σ2(Fo2) + (0.072P)2 + 0.6596P] where P = (Fo2 + 2Fc2)/3 |
11079 reflections | (Δ/σ)max < 0.001 |
284 parameters | Δρmax = 0.67 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
0 constraints |
Experimental. Analysis of 887 reflections having I/σ(I) > 12 and chosen from the full data set with CELL_NOW (Sheldrick, 2008) showed the crystal to belong to the triclinic system and to be twinned by a 180° rotation about the b* axis. The raw data were processed using the multi-component version ofSAINT under control of the two-component orientation file generated by CELL_NOW. |
x | y | z | Uiso*/Ueq | ||
S1 | 0.5206 (2) | 0.33776 (10) | 0.33099 (5) | 0.0286 (3) | |
N1 | 0.8655 (7) | 0.3466 (3) | 0.44900 (18) | 0.0270 (7) | |
N2 | 1.2403 (7) | 0.1661 (3) | 0.49127 (18) | 0.0263 (7) | |
N3 | 1.2790 (7) | −0.0317 (3) | 0.41350 (19) | 0.0272 (7) | |
H3 | 1.421 (13) | −0.086 (6) | 0.438 (3) | 0.054 (16)* | |
N4 | 1.1421 (7) | −0.0703 (4) | 0.3524 (2) | 0.0304 (8) | |
C1 | 0.7945 (8) | 0.2734 (4) | 0.3936 (2) | 0.0233 (8) | |
C2 | 1.0831 (8) | 0.2892 (4) | 0.4948 (2) | 0.0274 (9) | |
H2 | 1.127 (9) | 0.343 (4) | 0.534 (3) | 0.026 (11)* | |
C3 | 1.1622 (8) | 0.0951 (4) | 0.4342 (2) | 0.0223 (8) | |
C4 | 0.9406 (8) | 0.0320 (4) | 0.3344 (2) | 0.0294 (9) | |
H4 | 0.814 (11) | 0.013 (5) | 0.291 (3) | 0.046 (14)* | |
C5 | 0.9395 (8) | 0.1406 (4) | 0.3835 (2) | 0.0230 (8) | |
C6 | 0.4067 (9) | 0.5068 (4) | 0.3667 (2) | 0.0315 (9) | |
H6A | 0.398 (9) | 0.498 (4) | 0.423 (3) | 0.027 (11)* | |
H6B | 0.212 (11) | 0.525 (5) | 0.347 (3) | 0.042 (13)* | |
C7 | 0.5835 (9) | 0.6066 (4) | 0.3404 (2) | 0.0308 (9) | |
C8 | 0.7249 (10) | 0.6887 (5) | 0.3172 (3) | 0.0363 (10) | |
H8 | 0.851 (11) | 0.744 (5) | 0.304 (3) | 0.039 (14)* | |
S2 | 0.0250 (2) | 0.29312 (10) | 0.17167 (5) | 0.0281 (3) | |
N5 | 0.3598 (7) | 0.3327 (3) | 0.05226 (18) | 0.0287 (7) | |
N6 | 0.7361 (7) | 0.1642 (3) | 0.00878 (18) | 0.0265 (7) | |
N7 | 0.7867 (7) | −0.0506 (4) | 0.08603 (19) | 0.0272 (7) | |
H7 | 0.910 (12) | −0.098 (5) | 0.064 (3) | 0.044 (15)* | |
N8 | 0.6605 (7) | −0.1054 (4) | 0.1483 (2) | 0.0321 (8) | |
C9 | 0.2964 (8) | 0.2445 (4) | 0.1088 (2) | 0.0249 (8) | |
C10 | 0.5752 (8) | 0.2867 (4) | 0.0059 (2) | 0.0289 (9) | |
H10 | 0.620 (9) | 0.355 (4) | −0.034 (3) | 0.027 (11)* | |
C11 | 0.6642 (8) | 0.0790 (4) | 0.0663 (2) | 0.0237 (8) | |
C12 | 0.4571 (9) | −0.0095 (4) | 0.1677 (2) | 0.0294 (9) | |
H12 | 0.336 (11) | −0.019 (5) | 0.209 (3) | 0.038 (13)* | |
C13 | 0.4474 (8) | 0.1111 (4) | 0.1182 (2) | 0.0238 (8) | |
C14 | −0.0920 (9) | 0.4710 (5) | 0.1372 (3) | 0.0310 (9) | |
H14A | −0.112 (12) | 0.476 (5) | 0.080 (3) | 0.051 (15)* | |
H14B | −0.260 (11) | 0.490 (5) | 0.160 (3) | 0.039 (13)* | |
C15 | 0.0894 (9) | 0.5647 (4) | 0.1597 (2) | 0.0313 (9) | |
C16 | 0.2341 (10) | 0.6432 (5) | 0.1784 (3) | 0.0357 (10) | |
H16 | 0.356 (13) | 0.705 (6) | 0.189 (4) | 0.060 (17)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0232 (5) | 0.0360 (6) | 0.0253 (5) | −0.0025 (4) | −0.0072 (3) | 0.0030 (4) |
N1 | 0.0268 (17) | 0.0316 (17) | 0.0214 (16) | −0.0022 (14) | −0.0024 (12) | 0.0023 (13) |
N2 | 0.0234 (17) | 0.0315 (18) | 0.0235 (16) | −0.0043 (14) | −0.0059 (12) | 0.0021 (13) |
N3 | 0.0244 (17) | 0.0297 (18) | 0.0267 (17) | −0.0026 (15) | −0.0030 (13) | 0.0011 (14) |
N4 | 0.0275 (18) | 0.0326 (18) | 0.0310 (18) | −0.0032 (15) | −0.0040 (14) | −0.0034 (14) |
C1 | 0.0187 (18) | 0.031 (2) | 0.0200 (18) | −0.0064 (16) | −0.0005 (13) | 0.0033 (15) |
C2 | 0.026 (2) | 0.033 (2) | 0.0231 (19) | −0.0034 (17) | −0.0054 (15) | −0.0001 (16) |
C3 | 0.0193 (18) | 0.0276 (19) | 0.0202 (17) | −0.0059 (16) | −0.0001 (13) | 0.0025 (15) |
C4 | 0.025 (2) | 0.036 (2) | 0.028 (2) | −0.0055 (18) | −0.0035 (15) | −0.0031 (17) |
C5 | 0.0206 (19) | 0.0297 (19) | 0.0189 (18) | −0.0066 (16) | −0.0008 (13) | 0.0031 (14) |
C6 | 0.022 (2) | 0.039 (2) | 0.030 (2) | 0.0018 (18) | −0.0016 (15) | 0.0022 (18) |
C7 | 0.030 (2) | 0.032 (2) | 0.027 (2) | 0.0064 (19) | −0.0069 (16) | 0.0002 (17) |
C8 | 0.038 (3) | 0.035 (2) | 0.034 (2) | −0.001 (2) | −0.0024 (18) | 0.0028 (19) |
S2 | 0.0228 (5) | 0.0348 (5) | 0.0265 (5) | −0.0032 (4) | 0.0031 (3) | −0.0024 (4) |
N5 | 0.0277 (18) | 0.0336 (18) | 0.0238 (16) | −0.0024 (15) | 0.0009 (13) | 0.0002 (14) |
N6 | 0.0227 (17) | 0.0336 (18) | 0.0236 (16) | −0.0058 (14) | 0.0002 (12) | −0.0021 (13) |
N7 | 0.0226 (17) | 0.0315 (18) | 0.0263 (17) | −0.0009 (15) | 0.0033 (13) | 0.0002 (14) |
N8 | 0.0298 (19) | 0.0361 (19) | 0.0286 (18) | −0.0011 (16) | 0.0017 (13) | 0.0023 (14) |
C9 | 0.0211 (19) | 0.034 (2) | 0.0209 (18) | −0.0072 (16) | −0.0016 (14) | −0.0046 (15) |
C10 | 0.028 (2) | 0.033 (2) | 0.025 (2) | −0.0047 (18) | 0.0021 (15) | 0.0029 (17) |
C11 | 0.0201 (18) | 0.031 (2) | 0.0213 (18) | −0.0057 (16) | −0.0013 (14) | −0.0047 (15) |
C12 | 0.027 (2) | 0.035 (2) | 0.026 (2) | −0.0049 (18) | 0.0033 (16) | −0.0009 (17) |
C13 | 0.0183 (18) | 0.031 (2) | 0.0233 (18) | −0.0063 (16) | −0.0008 (14) | −0.0037 (15) |
C14 | 0.019 (2) | 0.040 (2) | 0.032 (2) | 0.0006 (18) | 0.0009 (16) | −0.0032 (18) |
C15 | 0.033 (2) | 0.034 (2) | 0.0223 (19) | 0.0065 (19) | 0.0027 (15) | −0.0002 (16) |
C16 | 0.041 (3) | 0.032 (2) | 0.033 (2) | −0.003 (2) | −0.0040 (19) | −0.0017 (18) |
S1—C1 | 1.747 (4) | S2—C9 | 1.743 (4) |
S1—C6 | 1.818 (4) | S2—C14 | 1.821 (4) |
N1—C1 | 1.322 (5) | N5—C9 | 1.339 (5) |
N1—C2 | 1.362 (5) | N5—C10 | 1.361 (5) |
N2—C2 | 1.334 (5) | N6—C10 | 1.331 (5) |
N2—C3 | 1.343 (5) | N6—C11 | 1.348 (5) |
N3—C3 | 1.359 (5) | N7—C11 | 1.347 (5) |
N3—N4 | 1.366 (5) | N7—N8 | 1.368 (5) |
N3—H3 | 0.90 (6) | N7—H7 | 0.81 (6) |
N4—C4 | 1.318 (5) | N8—C12 | 1.317 (6) |
C1—C5 | 1.407 (5) | C9—C13 | 1.403 (5) |
C2—H2 | 0.95 (5) | C10—H10 | 0.98 (5) |
C3—C5 | 1.406 (5) | C11—C13 | 1.399 (5) |
C4—C5 | 1.411 (6) | C12—C13 | 1.418 (6) |
C4—H4 | 1.03 (6) | C12—H12 | 0.93 (6) |
C6—C7 | 1.457 (6) | C14—C15 | 1.448 (6) |
C6—H6A | 0.98 (5) | C14—H14A | 1.00 (6) |
C6—H6B | 1.00 (5) | C14—H14B | 0.91 (5) |
C7—C8 | 1.194 (7) | C15—C16 | 1.187 (7) |
C8—H8 | 0.90 (5) | C16—H16 | 0.94 (6) |
C1—S1—C6 | 101.40 (19) | C9—S2—C14 | 101.5 (2) |
C1—N1—C2 | 117.5 (3) | C9—N5—C10 | 116.9 (3) |
C2—N2—C3 | 112.2 (3) | C10—N6—C11 | 112.1 (3) |
C3—N3—N4 | 110.9 (3) | C11—N7—N8 | 111.3 (3) |
C3—N3—H3 | 125 (4) | C11—N7—H7 | 128 (4) |
N4—N3—H3 | 124 (4) | N8—N7—H7 | 120 (4) |
C4—N4—N3 | 106.5 (3) | C12—N8—N7 | 106.3 (3) |
N1—C1—C5 | 120.4 (3) | N5—C9—C13 | 120.4 (4) |
N1—C1—S1 | 121.3 (3) | N5—C9—S2 | 120.7 (3) |
C5—C1—S1 | 118.2 (3) | C13—C9—S2 | 118.9 (3) |
N2—C2—N1 | 128.4 (4) | N6—C10—N5 | 128.8 (4) |
N2—C2—H2 | 116 (3) | N6—C10—H10 | 116 (3) |
N1—C2—H2 | 116 (3) | N5—C10—H10 | 115 (3) |
N2—C3—N3 | 127.8 (3) | N7—C11—N6 | 127.4 (4) |
N2—C3—C5 | 125.4 (3) | N7—C11—C13 | 107.0 (3) |
N3—C3—C5 | 106.8 (3) | N6—C11—C13 | 125.6 (4) |
N4—C4—C5 | 111.3 (3) | N8—C12—C13 | 110.9 (4) |
N4—C4—H4 | 114 (3) | N8—C12—H12 | 125 (3) |
C5—C4—H4 | 134 (3) | C13—C12—H12 | 124 (3) |
C3—C5—C1 | 115.9 (3) | C11—C13—C9 | 116.1 (3) |
C3—C5—C4 | 104.4 (3) | C11—C13—C12 | 104.5 (3) |
C1—C5—C4 | 139.6 (3) | C9—C13—C12 | 139.4 (4) |
C7—C6—S1 | 112.2 (3) | C15—C14—S2 | 113.1 (3) |
C7—C6—H6A | 112 (3) | C15—C14—H14A | 110 (3) |
S1—C6—H6A | 109 (2) | S2—C14—H14A | 109 (3) |
C7—C6—H6B | 116 (3) | C15—C14—H14B | 111 (3) |
S1—C6—H6B | 100 (3) | S2—C14—H14B | 103 (3) |
H6A—C6—H6B | 108 (4) | H14A—C14—H14B | 110 (4) |
C8—C7—C6 | 178.5 (4) | C16—C15—C14 | 178.8 (5) |
C7—C8—H8 | 172 (3) | C15—C16—H16 | 175 (4) |
C3—N3—N4—C4 | 0.2 (4) | C11—N7—N8—C12 | 0.1 (4) |
C2—N1—C1—C5 | 0.5 (6) | C10—N5—C9—C13 | −0.4 (5) |
C2—N1—C1—S1 | −179.4 (3) | C10—N5—C9—S2 | 179.8 (3) |
C6—S1—C1—N1 | 0.1 (4) | C14—S2—C9—N5 | −1.6 (3) |
C6—S1—C1—C5 | −179.8 (3) | C14—S2—C9—C13 | 178.6 (3) |
C3—N2—C2—N1 | −0.2 (6) | C11—N6—C10—N5 | 0.4 (6) |
C1—N1—C2—N2 | 0.4 (6) | C9—N5—C10—N6 | −0.2 (6) |
C2—N2—C3—N3 | 178.8 (4) | N8—N7—C11—N6 | 179.0 (3) |
C2—N2—C3—C5 | −0.9 (5) | N8—N7—C11—C13 | 0.1 (4) |
N4—N3—C3—N2 | −180.0 (4) | C10—N6—C11—N7 | −178.7 (4) |
N4—N3—C3—C5 | −0.3 (4) | C10—N6—C11—C13 | 0.1 (5) |
N3—N4—C4—C5 | −0.1 (5) | N7—N8—C12—C13 | −0.3 (4) |
N2—C3—C5—C1 | 1.7 (6) | N7—C11—C13—C9 | 178.3 (3) |
N3—C3—C5—C1 | −178.0 (3) | N6—C11—C13—C9 | −0.7 (5) |
N2—C3—C5—C4 | 179.9 (4) | N7—C11—C13—C12 | −0.3 (4) |
N3—C3—C5—C4 | 0.2 (4) | N6—C11—C13—C12 | −179.2 (3) |
N1—C1—C5—C3 | −1.4 (5) | N5—C9—C13—C11 | 0.8 (5) |
S1—C1—C5—C3 | 178.5 (3) | S2—C9—C13—C11 | −179.4 (3) |
N1—C1—C5—C4 | −178.7 (5) | N5—C9—C13—C12 | 178.7 (4) |
S1—C1—C5—C4 | 1.1 (7) | S2—C9—C13—C12 | −1.5 (6) |
N4—C4—C5—C3 | −0.1 (5) | N8—C12—C13—C11 | 0.4 (4) |
N4—C4—C5—C1 | 177.5 (5) | N8—C12—C13—C9 | −177.7 (4) |
C1—S1—C6—C7 | 79.3 (3) | C9—S2—C14—C15 | −76.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3···N2i | 0.90 (6) | 2.10 (6) | 2.972 (4) | 165 (5) |
N7—H7···N6ii | 0.81 (6) | 2.18 (6) | 2.965 (5) | 163 (5) |
Symmetry codes: (i) −x+3, −y, −z+1; (ii) −x+2, −y, −z. |
Acknowledgements
The support of NSF–MRI Grant No. 1228232 for the purchase of the diffractometer and Tulane University for support of the Tulane Crystallography Laboratory are gratefully acknowledged.
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