organic compounds
Ethyl 2-allyl-2-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)pent-4-enoate
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, and bDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
*Correspondence e-mail: elhafi.mohamed1@gmail.com
In the title molecule, C16H20N4O2, the dihedral angle between the planes of the fused rings is 2.26 (8)°. In the crystal, [10] chains of molecules linked by C—H⋯O and C—H⋯N hydrogen bonds arise, which are further linked by weak C—H⋯π interactions.
Keywords: crystal structure; triazolopyrimidine; alkylation; hydrogen bond.
CCDC reference: 1571230
Structure description
Triazolopyrimidine derivatives display various pharmacological properties, including anti-inflammatory (Ashour et al., 2013), anticancer (Hoffmann et al., 2017) and antibacterial (Mabkhot et al., 2016) activities. The present work is a continuation of our structural studies of triazolopyrimidine derivatives (Lahmidi et al., 2016) and reports the synthesis and structure of the title compound, ethyl 2-allyl-2-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)pent-4-enoate (Fig. 1).
The bicyclic unit is slightly nonplanar, as indicated by the dihedral angle of 2.26 (8)° between the planes of the five- and six-membered rings. In the crystal, molecules form centrosymmetric dimers through complementary C1—H1⋯O1i hydrogen bonds, which are connected into [10] chains by C16—H16A⋯N4ii hydrogen bonds (Table 1 and Fig. 2). The chains are connected by C12—H12⋯Cg1iii (Cg1 is the centroid of the C1/N3/C2/N1/N2 ring) interactions (Table 1 and Figs. 2 and 3).
Synthesis and crystallization
Allyl bromide (0.22 ml, 2.5 mmol), potassium carbonate (0.34 g, 2.5 mmol) and a catalytic quantity of tetra-n-butylammonium iodide were added to a solution of ethyl 2-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)acetate (0.5 g, 2.3 mmol) in DMF (15 ml). The mixture was stirred at room temperature for 48 h. The solution was filtered and the solvent removed under reduced pressure. The resulting residue was purified by (EtOAc–hexane 1/9 v/v). The title compound was recrystallized from an ethanol solution at room temperature to yield colourless plates (yield 30%; m.p. 364–366 K).
Refinement
Crystal and . The H atoms were located in difference maps and their positions and Uiso(H) values were refined freely.
data are presented in Table 2Structural data
CCDC reference: 1571230
https://doi.org/10.1107/S2414314617012433/hb4166sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617012433/hb4166Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314617012433/hb4166Isup3.cdx
Supporting information file. DOI: https://doi.org/10.1107/S2414314617012433/hb4166Isup4.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 (Bruker, 2016).C16H20N4O2 | F(000) = 640 |
Mr = 300.36 | Dx = 1.254 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
a = 10.0937 (9) Å | Cell parameters from 4361 reflections |
b = 13.4926 (12) Å | θ = 2.3–27.5° |
c = 11.6936 (11) Å | µ = 0.09 mm−1 |
β = 92.999 (1)° | T = 100 K |
V = 1590.4 (2) Å3 | Plate, colourless |
Z = 4 | 0.30 × 0.24 × 0.07 mm |
Bruker SMART APEX CCD diffractometer | 3914 independent reflections |
Radiation source: fine-focus sealed tube | 2819 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 8.3333 pixels mm-1 | θmax = 28.3°, θmin = 2.3° |
φ and ω scans | h = −13→13 |
Absorption correction: multi-scan (SADABS; Bruker, 2016) | k = −17→17 |
Tmin = 0.83, Tmax = 0.99 | l = −15→15 |
14774 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)] = 0.042 | Hydrogen site location: difference Fourier map |
wR(F2) = 0.111 | All H-atom parameters refined |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0627P)2] where P = (Fo2 + 2Fc2)/3 |
3914 reflections | (Δ/σ)max < 0.001 |
279 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.18 e Å−3 |
Experimental. The diffraction data were collected in three sets of 363 frames (0.5° width in ω) at φ = 0, 120 and 240°. A scan time of 40 sec/frame was used. |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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 | ||
O1 | 0.37418 (8) | 0.59703 (6) | 0.81629 (7) | 0.0269 (2) | |
O2 | 0.52312 (8) | 0.53189 (6) | 0.70030 (7) | 0.0237 (2) | |
N1 | 0.45281 (9) | 0.32484 (7) | 0.77637 (8) | 0.0195 (2) | |
N2 | 0.47572 (10) | 0.37149 (8) | 0.87926 (8) | 0.0231 (2) | |
N3 | 0.58922 (10) | 0.22459 (8) | 0.87571 (9) | 0.0252 (3) | |
N4 | 0.51065 (10) | 0.17365 (7) | 0.68593 (9) | 0.0230 (2) | |
C1 | 0.55721 (12) | 0.30760 (9) | 0.93342 (11) | 0.0245 (3) | |
H1 | 0.5901 (13) | 0.3219 (10) | 1.0103 (12) | 0.027 (4)* | |
C2 | 0.52088 (11) | 0.23590 (9) | 0.77578 (10) | 0.0207 (3) | |
C3 | 0.43401 (12) | 0.20285 (9) | 0.59705 (11) | 0.0226 (3) | |
C4 | 0.36816 (12) | 0.29598 (9) | 0.59266 (10) | 0.0210 (3) | |
H4 | 0.3144 (12) | 0.3147 (9) | 0.5254 (11) | 0.019 (3)* | |
C5 | 0.37784 (11) | 0.35921 (8) | 0.68375 (10) | 0.0189 (3) | |
C6 | 0.41670 (16) | 0.13343 (11) | 0.49806 (12) | 0.0309 (3) | |
H6A | 0.343 (2) | 0.0885 (15) | 0.5148 (17) | 0.068 (6)* | |
H6B | 0.4950 (19) | 0.0955 (13) | 0.4883 (15) | 0.057 (5)* | |
H6C | 0.3894 (18) | 0.1684 (13) | 0.4266 (16) | 0.057 (5)* | |
C7 | 0.31002 (11) | 0.45886 (8) | 0.69306 (10) | 0.0198 (3) | |
C8 | 0.18878 (12) | 0.44847 (9) | 0.76874 (11) | 0.0222 (3) | |
H8A | 0.2226 (13) | 0.4273 (10) | 0.8461 (12) | 0.023 (3)* | |
H8B | 0.1481 (13) | 0.5139 (10) | 0.7775 (11) | 0.026 (3)* | |
C9 | 0.08519 (13) | 0.37797 (11) | 0.72205 (11) | 0.0292 (3) | |
H9 | 0.1090 (14) | 0.3062 (11) | 0.7130 (12) | 0.036 (4)* | |
C10 | −0.03729 (15) | 0.40450 (14) | 0.69308 (13) | 0.0409 (4) | |
H10A | −0.1047 (16) | 0.3565 (12) | 0.6617 (14) | 0.047 (5)* | |
H10B | −0.0668 (18) | 0.4742 (14) | 0.7006 (15) | 0.058 (5)* | |
C11 | 0.26878 (13) | 0.49788 (9) | 0.57071 (10) | 0.0219 (3) | |
H11A | 0.2026 (14) | 0.4522 (11) | 0.5368 (12) | 0.032 (4)* | |
H11B | 0.3478 (13) | 0.4967 (10) | 0.5237 (12) | 0.027 (4)* | |
C12 | 0.21439 (14) | 0.60122 (10) | 0.57129 (11) | 0.0274 (3) | |
H12 | 0.1231 (15) | 0.6095 (11) | 0.5947 (12) | 0.036 (4)* | |
C13 | 0.27982 (17) | 0.67987 (11) | 0.54030 (14) | 0.0383 (4) | |
H13A | 0.373 (2) | 0.6753 (14) | 0.5132 (16) | 0.065 (6)* | |
H13B | 0.2415 (16) | 0.7449 (13) | 0.5415 (14) | 0.051 (5)* | |
C14 | 0.40517 (12) | 0.53624 (8) | 0.74715 (10) | 0.0213 (3) | |
C15 | 0.62385 (14) | 0.60166 (10) | 0.74566 (13) | 0.0290 (3) | |
H15A | 0.5776 (15) | 0.6664 (11) | 0.7541 (12) | 0.035 (4)* | |
H15B | 0.6865 (14) | 0.6049 (11) | 0.6882 (13) | 0.032 (4)* | |
C16 | 0.68866 (14) | 0.56365 (12) | 0.85544 (13) | 0.0329 (3) | |
H16A | 0.7608 (15) | 0.6089 (11) | 0.8776 (13) | 0.038 (4)* | |
H16B | 0.7315 (16) | 0.4978 (13) | 0.8408 (13) | 0.041 (4)* | |
H16C | 0.6263 (15) | 0.5586 (11) | 0.9181 (13) | 0.039 (4)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0307 (5) | 0.0223 (5) | 0.0272 (5) | 0.0025 (4) | −0.0037 (4) | −0.0072 (4) |
O2 | 0.0236 (4) | 0.0226 (5) | 0.0246 (5) | −0.0033 (3) | −0.0010 (4) | −0.0015 (3) |
N1 | 0.0227 (5) | 0.0183 (5) | 0.0173 (5) | −0.0003 (4) | −0.0009 (4) | −0.0019 (4) |
N2 | 0.0262 (5) | 0.0244 (5) | 0.0183 (5) | −0.0010 (4) | −0.0035 (4) | −0.0021 (4) |
N3 | 0.0257 (6) | 0.0244 (6) | 0.0251 (6) | 0.0010 (4) | −0.0025 (4) | 0.0015 (4) |
N4 | 0.0257 (5) | 0.0197 (5) | 0.0238 (6) | 0.0005 (4) | 0.0026 (4) | −0.0009 (4) |
C1 | 0.0258 (6) | 0.0266 (7) | 0.0206 (7) | −0.0005 (5) | −0.0027 (5) | 0.0013 (5) |
C2 | 0.0198 (6) | 0.0183 (6) | 0.0240 (6) | 0.0010 (5) | 0.0018 (5) | 0.0014 (5) |
C3 | 0.0243 (6) | 0.0204 (6) | 0.0234 (6) | −0.0017 (5) | 0.0048 (5) | −0.0018 (5) |
C4 | 0.0235 (6) | 0.0211 (6) | 0.0183 (6) | −0.0009 (5) | 0.0000 (5) | −0.0004 (5) |
C5 | 0.0192 (6) | 0.0200 (6) | 0.0176 (6) | −0.0008 (4) | 0.0013 (5) | 0.0006 (5) |
C6 | 0.0408 (8) | 0.0251 (7) | 0.0267 (7) | 0.0039 (6) | 0.0008 (6) | −0.0070 (6) |
C7 | 0.0218 (6) | 0.0189 (6) | 0.0185 (6) | 0.0015 (5) | −0.0021 (5) | −0.0022 (5) |
C8 | 0.0238 (6) | 0.0236 (7) | 0.0190 (6) | 0.0032 (5) | −0.0003 (5) | −0.0019 (5) |
C9 | 0.0294 (7) | 0.0353 (8) | 0.0234 (7) | −0.0056 (6) | 0.0054 (5) | −0.0044 (6) |
C10 | 0.0302 (8) | 0.0600 (11) | 0.0319 (8) | −0.0114 (7) | −0.0046 (6) | 0.0064 (7) |
C11 | 0.0244 (6) | 0.0226 (6) | 0.0184 (6) | 0.0017 (5) | −0.0020 (5) | −0.0011 (5) |
C12 | 0.0316 (7) | 0.0284 (7) | 0.0217 (7) | 0.0073 (6) | −0.0027 (5) | 0.0004 (5) |
C13 | 0.0447 (9) | 0.0251 (8) | 0.0441 (9) | 0.0024 (7) | −0.0063 (7) | 0.0061 (6) |
C14 | 0.0252 (6) | 0.0180 (6) | 0.0204 (6) | 0.0022 (5) | −0.0032 (5) | 0.0010 (5) |
C15 | 0.0272 (7) | 0.0262 (7) | 0.0332 (8) | −0.0088 (6) | −0.0008 (6) | 0.0000 (6) |
C16 | 0.0257 (7) | 0.0413 (9) | 0.0312 (8) | −0.0088 (6) | −0.0025 (6) | −0.0015 (6) |
O1—C14 | 1.2044 (14) | C7—C11 | 1.5605 (16) |
O2—C14 | 1.3377 (15) | C8—C9 | 1.4954 (18) |
O2—C15 | 1.4645 (15) | C8—H8A | 0.992 (14) |
N1—N2 | 1.3668 (14) | C8—H8B | 0.981 (14) |
N1—C5 | 1.3693 (15) | C9—C10 | 1.314 (2) |
N1—C2 | 1.3830 (15) | C9—H9 | 1.004 (15) |
N2—C1 | 1.3290 (16) | C10—H10A | 0.995 (17) |
N3—C2 | 1.3342 (15) | C10—H10B | 0.992 (18) |
N3—C1 | 1.3553 (16) | C11—C12 | 1.4987 (18) |
N4—C3 | 1.3228 (16) | C11—H11A | 0.977 (14) |
N4—C2 | 1.3449 (16) | C11—H11B | 0.992 (15) |
C1—H1 | 0.962 (14) | C12—C13 | 1.311 (2) |
C3—C4 | 1.4211 (17) | C12—H12 | 0.981 (15) |
C3—C6 | 1.4922 (18) | C13—H13A | 1.01 (2) |
C4—C5 | 1.3642 (16) | C13—H13B | 0.960 (17) |
C4—H4 | 0.965 (13) | C15—C16 | 1.500 (2) |
C5—C7 | 1.5154 (16) | C15—H15A | 0.998 (15) |
C6—H6A | 0.99 (2) | C15—H15B | 0.947 (15) |
C6—H6B | 0.954 (19) | C16—H16A | 0.976 (16) |
C6—H6C | 0.986 (18) | C16—H16B | 1.007 (17) |
C7—C14 | 1.5326 (16) | C16—H16C | 0.993 (16) |
C7—C8 | 1.5536 (17) | ||
C14—O2—C15 | 116.06 (10) | C9—C8—H8B | 108.8 (8) |
N2—N1—C5 | 126.97 (10) | C7—C8—H8B | 109.0 (8) |
N2—N1—C2 | 110.05 (9) | H8A—C8—H8B | 106.8 (11) |
C5—N1—C2 | 122.96 (10) | C10—C9—C8 | 123.45 (15) |
C1—N2—N1 | 101.11 (10) | C10—C9—H9 | 117.5 (8) |
C2—N3—C1 | 102.46 (10) | C8—C9—H9 | 119.0 (8) |
C3—N4—C2 | 116.47 (10) | C9—C10—H10A | 122.2 (9) |
N2—C1—N3 | 117.16 (11) | C9—C10—H10B | 121.2 (10) |
N2—C1—H1 | 119.4 (8) | H10A—C10—H10B | 116.6 (14) |
N3—C1—H1 | 123.5 (8) | C12—C11—C7 | 112.95 (10) |
N3—C2—N4 | 128.89 (11) | C12—C11—H11A | 110.2 (8) |
N3—C2—N1 | 109.21 (10) | C7—C11—H11A | 107.6 (8) |
N4—C2—N1 | 121.86 (11) | C12—C11—H11B | 108.8 (8) |
N4—C3—C4 | 123.02 (11) | C7—C11—H11B | 108.6 (8) |
N4—C3—C6 | 117.55 (11) | H11A—C11—H11B | 108.6 (11) |
C4—C3—C6 | 119.43 (11) | C13—C12—C11 | 124.19 (14) |
C5—C4—C3 | 120.69 (11) | C13—C12—H12 | 118.6 (9) |
C5—C4—H4 | 119.1 (7) | C11—C12—H12 | 117.1 (9) |
C3—C4—H4 | 120.2 (8) | C12—C13—H13A | 121.9 (11) |
C4—C5—N1 | 114.82 (10) | C12—C13—H13B | 121.8 (10) |
C4—C5—C7 | 126.65 (11) | H13A—C13—H13B | 116.3 (14) |
N1—C5—C7 | 118.47 (10) | O1—C14—O2 | 124.94 (11) |
C3—C6—H6A | 106.9 (11) | O1—C14—C7 | 124.18 (11) |
C3—C6—H6B | 111.5 (11) | O2—C14—C7 | 110.67 (10) |
H6A—C6—H6B | 109.3 (15) | O2—C15—C16 | 110.70 (11) |
C3—C6—H6C | 111.9 (10) | O2—C15—H15A | 106.2 (8) |
H6A—C6—H6C | 106.4 (15) | C16—C15—H15A | 113.6 (8) |
H6B—C6—H6C | 110.7 (14) | O2—C15—H15B | 104.4 (9) |
C5—C7—C14 | 111.00 (9) | C16—C15—H15B | 110.2 (9) |
C5—C7—C8 | 109.46 (10) | H15A—C15—H15B | 111.3 (12) |
C14—C7—C8 | 108.77 (9) | C15—C16—H16A | 107.4 (9) |
C5—C7—C11 | 109.47 (9) | C15—C16—H16B | 109.2 (9) |
C14—C7—C11 | 106.26 (10) | H16A—C16—H16B | 106.1 (13) |
C8—C7—C11 | 111.86 (9) | C15—C16—H16C | 112.9 (9) |
C9—C8—C7 | 113.95 (10) | H16A—C16—H16C | 109.9 (12) |
C9—C8—H8A | 110.5 (8) | H16B—C16—H16C | 111.1 (13) |
C7—C8—H8A | 107.6 (8) | ||
C5—N1—N2—C1 | −177.62 (11) | N1—C5—C7—C14 | 45.52 (14) |
C2—N1—N2—C1 | 0.51 (12) | C4—C5—C7—C8 | 102.45 (13) |
N1—N2—C1—N3 | 0.09 (14) | N1—C5—C7—C8 | −74.56 (13) |
C2—N3—C1—N2 | −0.64 (14) | C4—C5—C7—C11 | −20.49 (16) |
C1—N3—C2—N4 | −177.09 (12) | N1—C5—C7—C11 | 162.50 (10) |
C1—N3—C2—N1 | 0.91 (12) | C5—C7—C8—C9 | −61.13 (13) |
C3—N4—C2—N3 | 179.07 (12) | C14—C7—C8—C9 | 177.43 (11) |
C3—N4—C2—N1 | 1.30 (17) | C11—C7—C8—C9 | 60.38 (14) |
N2—N1—C2—N3 | −0.95 (13) | C7—C8—C9—C10 | −118.44 (14) |
C5—N1—C2—N3 | 177.27 (10) | C5—C7—C11—C12 | −173.66 (10) |
N2—N1—C2—N4 | 177.22 (10) | C14—C7—C11—C12 | −53.73 (14) |
C5—N1—C2—N4 | −4.56 (18) | C8—C7—C11—C12 | 64.83 (14) |
C2—N4—C3—C4 | 2.01 (17) | C7—C11—C12—C13 | 104.71 (15) |
C2—N4—C3—C6 | −177.65 (11) | C15—O2—C14—O1 | 5.68 (17) |
N4—C3—C4—C5 | −2.33 (18) | C15—O2—C14—C7 | −179.35 (9) |
C6—C3—C4—C5 | 177.32 (12) | C5—C7—C14—O1 | −139.28 (12) |
C3—C4—C5—N1 | −0.75 (17) | C8—C7—C14—O1 | −18.80 (16) |
C3—C4—C5—C7 | −177.85 (11) | C11—C7—C14—O1 | 101.79 (13) |
N2—N1—C5—C4 | −178.06 (11) | C5—C7—C14—O2 | 45.70 (13) |
C2—N1—C5—C4 | 4.03 (16) | C8—C7—C14—O2 | 166.19 (9) |
N2—N1—C5—C7 | −0.71 (17) | C11—C7—C14—O2 | −73.23 (11) |
C2—N1—C5—C7 | −178.61 (10) | C14—O2—C15—C16 | 80.88 (14) |
C4—C5—C7—C14 | −137.48 (12) |
D—H···A | D—H | H···A | D···A | D—H···A |
C1—H1···O1i | 0.962 (14) | 2.315 (14) | 3.2388 (15) | 160.7 (11) |
C16—H16A···N4ii | 0.976 (16) | 2.610 (16) | 3.4354 (18) | 142.4 (12) |
C12—H12···Cg1iii | 0.981 (15) | 2.955 (15) | 3.6559 (15) | 129.3 (11) |
Symmetry codes: (i) −x+1, −y+1, −z+2; (ii) −x+3/2, y+1/2, −z+3/2; (iii) −x+1/2, y+1/2, −z+3/2. |
Acknowledgements
JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.
References
Ashour, H., Shaaban, O., Rizk, O. & Ashmawy, I. (2013). Eur. J. Med. Chem. 62, 341–351. Web of Science CrossRef CAS PubMed Google Scholar
Brandenburg, K. & Putz, H. (2012). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2016). APEX3, SADABS and SAINT. Bruker ACS Inc., Madison, Wisconsin, USA. Google Scholar
Hoffmann, K., Wisniewska, J., Wojtczak, A., Sitkowski, J., Denslow, A., Wietrzyk, J., Jakubowski, M. & Lakomska, I. (2017). J. Inorg. Biochem. 172, 34–45. Web of Science CSD CrossRef CAS PubMed Google Scholar
Lahmidi, S., Sebbar, N. K., Harmaoui, A., Ouzidan, Y., Essassi, E. M. & Mague, J. T. (2016). IUCrData, 1, x161946. Google Scholar
Mabkhot, Y. N., Alatibi, F., El- Sayed, N. N. E., Kheder, N. A. & Al- Showiman, S. S. (2016). Molecules, 21, 268–278. Web of Science PubMed Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015a). Acta Cryst. A71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2015b). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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