organic compounds
5-(2-Ethoxy-4-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine
aDepartment of Studies in Chemistry, Manasagangotri, University of Mysore, Mysore, Karnataka, India, bPURSE Lab, Mangalagangotri, Mangalore University, Mangaluru 574 199, India, cDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore, Karnataka, India, and dDepartment of Material Science, Mangalore University, Mangaluru 574 199, India
*Correspondence e-mail: rangappaks@gmail.com
In the title compound, C13H11FN4O, the dihedral angle between the triazolopyrimidine ring system and fluorophenyl ring is 39.16 (12)°. In the crystal, C—H⋯N hydrogen bonds link the molecules resulting in R22(8) ring motifs and C(8) chain motifs.
Keywords: crystal structure; triazoles; intermolecular hydrogen bonds.
CCDC reference: 1515262
Structure description
1,2,4-Triazolo[1,5-a]pyrimidine derivatives are used in the field of pharmaceutics, agriculture and other areas (Mopper & Zhou, 1990). As part of our work on the synthesis and determination of 1,2,4-triazolo[1,5-a]pyrimidine derivatives (Gilandoust et al., 2016), the title compound is reported here.
Fig. 1 represents the ORTEP drawing of the title compound of which the geometric parameters (bond lengths and bond angles) are in the normal range. The dihedral angle between the triazolopyrimidine and fluorophenyl rings is 39.16 (12)°. An intramolecular C17—H17⋯O1 contact (Table 1) is observed.
|
The , Table 1). The C5—H5⋯N4 and C16—H16⋯N2 hydrogen bonds lead to the formation of infinite chains along the b axis [C(8) chain motifs] and inversion dimers [R22(8) ring motifs], respectively.
features C—H⋯N hydrogen bonds (Fig. 2Synthesis and crystallization
5-Bromo-[1,2,4]-triazolo[1,5-a]pyrimidines (1 mmol), 2-ethoxy-4-fluorobenzenboronic acid (1.2 mmol) and K2CO3 (3 mmol) were added to a mixture of ethanol, water and 1,4-dioxan in the ratio (1:1:5). The reaction mixture was stirred in a sealed tube for 15 min in the presence of nitrogen gas to create an inert atmosphere after which the catalyst [PdCl2(PPh3)2] was added (0.1 mmol). The reaction mass was heated to 120–130°C for 35 min in a sealed tube and the progress of the reaction was monitored by TLC. The resultant mixture was filtered through a Celite bed and the filtrate was concentrated under reduced pressure to remove the ethanol by using a rotary evaporator. The reaction mass was extracted with ethyl acetate followed by a brine wash and dried over anhydrous sodium sulfate. The organic layer was evaporated under reduced pressure to get the crude product, which was purified by using 60:120 mesh silica gel and EtOAc:hexane as (40:60 ml) to get the desired triazolopyrimidine as a white solid. Good quality single crystals suitable for X-ray diffraction studies were obtained by the slow evaporation method using ethanol as a solvent.
Refinement
Crystal data, data collection and structure .
details are summarized in Table 2Structural data
CCDC reference: 1515262
https://doi.org/10.1107/S2414314616017703/vm4017sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017703/vm4017Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2414314616017703/vm4017Isup3.cml
Data collection: CrystalClear SM Expert (Rigaku, 2011); cell
CrystalClear SM Expert (Rigaku, 2011); data reduction: CrystalClear SM Expert (Rigaku, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).C13H11FN4O | F(000) = 536 |
Mr = 258.26 | Dx = 1.400 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
a = 3.9166 (3) Å | Cell parameters from 2171 reflections |
b = 16.6608 (11) Å | θ = 2.2–25.0° |
c = 18.8096 (14) Å | µ = 0.10 mm−1 |
β = 93.232 (7)° | T = 293 K |
V = 1225.44 (16) Å3 | Block, yellow |
Z = 4 | 0.32 × 0.23 × 0.21 mm |
Rigaku Saturn724+ diffractometer | Rint = 0.059 |
profile data from ω–scans | θmax = 25.0°, θmin = 2.2° |
Absorption correction: multi-scan (NUMABS; Rigaku, 1999) | h = −4→3 |
Tmin = 0.966, Tmax = 0.979 | k = −19→19 |
10165 measured reflections | l = −22→22 |
2171 independent reflections | 2171 standard reflections |
1458 reflections with I > 2σ(I) |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.061 | w = 1/[σ2(Fo2) + (0.0817P)2 + 0.3483P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.182 | (Δ/σ)max < 0.001 |
S = 1.08 | Δρmax = 0.24 e Å−3 |
2171 reflections | Δρmin = −0.26 e Å−3 |
174 parameters | Extinction correction: SHELXL2014 (Sheldrick, 2015), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.023 (4) |
Primary atom site location: iterative |
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. |
x | y | z | Uiso*/Ueq | ||
F1 | 0.5117 (7) | 0.35926 (13) | 0.52220 (10) | 0.1067 (9) | |
O1 | 0.7212 (5) | 0.32471 (10) | 0.77097 (10) | 0.0567 (6) | |
N1 | 1.1380 (5) | 0.55271 (12) | 0.91136 (11) | 0.0459 (6) | |
N2 | 1.1990 (6) | 0.60040 (14) | 0.97014 (12) | 0.0574 (7) | |
N3 | 0.8590 (5) | 0.56069 (12) | 0.79604 (11) | 0.0464 (6) | |
N4 | 0.8923 (6) | 0.66793 (13) | 0.88210 (12) | 0.0575 (7) | |
C1 | 0.7414 (9) | 0.4662 (2) | 0.59031 (16) | 0.0701 (9) | |
H1 | 0.7509 | 0.4977 | 0.5497 | 0.084* | |
C2 | 0.8464 (7) | 0.49545 (17) | 0.65655 (15) | 0.0573 (8) | |
H2 | 0.9233 | 0.5482 | 0.6605 | 0.069* | |
C3 | 0.8405 (7) | 0.44865 (15) | 0.71738 (14) | 0.0468 (7) | |
C4 | 0.7224 (7) | 0.36906 (16) | 0.71033 (14) | 0.0503 (7) | |
C5 | 0.6084 (8) | 0.33987 (18) | 0.64441 (16) | 0.0607 (8) | |
H5 | 0.5237 | 0.2879 | 0.6395 | 0.073* | |
C6 | 0.6231 (9) | 0.3892 (2) | 0.58674 (17) | 0.0707 (9) | |
C7 | 0.5874 (8) | 0.24438 (16) | 0.76772 (18) | 0.0627 (9) | |
H7A | 0.7172 | 0.2116 | 0.7363 | 0.075* | |
H7B | 0.3500 | 0.2448 | 0.7500 | 0.075* | |
C8 | 0.6178 (9) | 0.2119 (2) | 0.8419 (2) | 0.0806 (11) | |
H8A | 0.4932 | 0.2458 | 0.8727 | 0.121* | |
H8B | 0.8542 | 0.2106 | 0.8584 | 0.121* | |
H8C | 0.5253 | 0.1586 | 0.8424 | 0.121* | |
C9 | 0.9482 (6) | 0.48491 (14) | 0.78707 (13) | 0.0436 (6) | |
C11 | 0.9540 (6) | 0.59429 (15) | 0.85917 (13) | 0.0447 (7) | |
C13 | 1.0413 (8) | 0.66697 (18) | 0.94821 (16) | 0.0619 (8) | |
H13 | 1.0338 | 0.7117 | 0.9777 | 0.074* | |
C16 | 1.2387 (7) | 0.47580 (16) | 0.90249 (15) | 0.0499 (7) | |
H16 | 1.3677 | 0.4485 | 0.9378 | 0.060* | |
C17 | 1.1421 (7) | 0.44085 (16) | 0.83985 (14) | 0.0494 (7) | |
H17 | 1.2026 | 0.3879 | 0.8312 | 0.059* |
U11 | U22 | U33 | U12 | U13 | U23 | |
F1 | 0.152 (2) | 0.0993 (17) | 0.0656 (13) | 0.0004 (14) | −0.0248 (13) | −0.0214 (11) |
O1 | 0.0669 (13) | 0.0402 (10) | 0.0630 (13) | −0.0063 (9) | 0.0050 (10) | −0.0024 (9) |
N1 | 0.0472 (13) | 0.0443 (13) | 0.0459 (13) | −0.0022 (10) | −0.0002 (10) | 0.0059 (10) |
N2 | 0.0691 (17) | 0.0534 (15) | 0.0491 (14) | −0.0032 (12) | −0.0021 (12) | 0.0003 (11) |
N3 | 0.0482 (13) | 0.0396 (12) | 0.0511 (13) | 0.0002 (9) | −0.0006 (11) | 0.0040 (9) |
N4 | 0.0680 (17) | 0.0449 (14) | 0.0591 (15) | 0.0030 (11) | −0.0016 (13) | −0.0019 (11) |
C1 | 0.078 (2) | 0.078 (2) | 0.0537 (19) | 0.0043 (18) | −0.0027 (17) | 0.0062 (16) |
C2 | 0.0580 (18) | 0.0527 (17) | 0.0609 (18) | 0.0015 (13) | −0.0006 (14) | 0.0026 (14) |
C3 | 0.0402 (14) | 0.0441 (15) | 0.0557 (16) | 0.0026 (11) | 0.0000 (12) | −0.0014 (12) |
C4 | 0.0502 (16) | 0.0438 (15) | 0.0572 (17) | 0.0068 (12) | 0.0053 (13) | −0.0050 (13) |
C5 | 0.0619 (19) | 0.0533 (18) | 0.067 (2) | 0.0035 (14) | 0.0006 (16) | −0.0133 (15) |
C6 | 0.079 (2) | 0.075 (2) | 0.0562 (19) | 0.0072 (18) | −0.0095 (17) | −0.0152 (17) |
C7 | 0.0519 (17) | 0.0401 (15) | 0.097 (2) | −0.0062 (13) | 0.0091 (16) | −0.0051 (15) |
C8 | 0.070 (2) | 0.0553 (19) | 0.116 (3) | −0.0083 (16) | 0.007 (2) | 0.0229 (19) |
C9 | 0.0376 (14) | 0.0410 (14) | 0.0521 (15) | −0.0030 (11) | 0.0025 (11) | 0.0028 (11) |
C11 | 0.0452 (15) | 0.0416 (14) | 0.0471 (15) | −0.0040 (11) | 0.0015 (12) | 0.0068 (12) |
C13 | 0.078 (2) | 0.0495 (18) | 0.0576 (18) | −0.0016 (15) | 0.0008 (16) | −0.0050 (14) |
C16 | 0.0480 (16) | 0.0453 (15) | 0.0559 (17) | 0.0032 (12) | −0.0011 (13) | 0.0113 (13) |
C17 | 0.0456 (15) | 0.0415 (15) | 0.0610 (18) | 0.0033 (11) | 0.0020 (13) | 0.0055 (12) |
F1—C6 | 1.361 (3) | C3—C4 | 1.408 (4) |
O1—C4 | 1.359 (3) | C3—C9 | 1.483 (3) |
O1—C7 | 1.437 (3) | C4—C5 | 1.382 (4) |
N1—N2 | 1.371 (3) | C5—H5 | 0.9300 |
N1—C11 | 1.372 (3) | C5—C6 | 1.365 (4) |
N1—C16 | 1.354 (3) | C7—H7A | 0.9700 |
N2—C13 | 1.324 (4) | C7—H7B | 0.9700 |
N3—C9 | 1.323 (3) | C7—C8 | 1.495 (4) |
N3—C11 | 1.346 (3) | C8—H8A | 0.9600 |
N4—C11 | 1.327 (3) | C8—H8B | 0.9600 |
N4—C13 | 1.344 (3) | C8—H8C | 0.9600 |
C1—H1 | 0.9300 | C9—C17 | 1.420 (3) |
C1—C2 | 1.379 (4) | C13—H13 | 0.9300 |
C1—C6 | 1.364 (5) | C16—H16 | 0.9300 |
C2—H2 | 0.9300 | C16—C17 | 1.349 (4) |
C2—C3 | 1.386 (4) | C17—H17 | 0.9300 |
C4—O1—C7 | 119.3 (2) | O1—C7—H7B | 110.4 |
N2—N1—C11 | 110.2 (2) | O1—C7—C8 | 106.7 (2) |
C16—N1—N2 | 127.5 (2) | H7A—C7—H7B | 108.6 |
C16—N1—C11 | 122.3 (2) | C8—C7—H7A | 110.4 |
C13—N2—N1 | 100.2 (2) | C8—C7—H7B | 110.4 |
C9—N3—C11 | 116.6 (2) | C7—C8—H8A | 109.5 |
C11—N4—C13 | 102.3 (2) | C7—C8—H8B | 109.5 |
C2—C1—H1 | 121.3 | C7—C8—H8C | 109.5 |
C6—C1—H1 | 121.3 | H8A—C8—H8B | 109.5 |
C6—C1—C2 | 117.4 (3) | H8A—C8—H8C | 109.5 |
C1—C2—H2 | 119.0 | H8B—C8—H8C | 109.5 |
C1—C2—C3 | 121.9 (3) | N3—C9—C3 | 115.9 (2) |
C3—C2—H2 | 119.0 | N3—C9—C17 | 122.6 (2) |
C2—C3—C4 | 118.2 (2) | C17—C9—C3 | 121.4 (2) |
C2—C3—C9 | 118.9 (2) | N3—C11—N1 | 121.9 (2) |
C4—C3—C9 | 122.9 (2) | N4—C11—N1 | 109.4 (2) |
O1—C4—C3 | 116.7 (2) | N4—C11—N3 | 128.7 (2) |
O1—C4—C5 | 123.0 (3) | N2—C13—N4 | 118.0 (3) |
C5—C4—C3 | 120.2 (3) | N2—C13—H13 | 121.0 |
C4—C5—H5 | 120.8 | N4—C13—H13 | 121.0 |
C6—C5—C4 | 118.4 (3) | N1—C16—H16 | 121.7 |
C6—C5—H5 | 120.8 | C17—C16—N1 | 116.5 (2) |
F1—C6—C1 | 118.6 (3) | C17—C16—H16 | 121.7 |
F1—C6—C5 | 117.5 (3) | C9—C17—H17 | 120.0 |
C1—C6—C5 | 123.8 (3) | C16—C17—C9 | 120.0 (2) |
O1—C7—H7A | 110.4 | C16—C17—H17 | 120.0 |
O1—C4—C5—C6 | −179.5 (3) | C4—C5—C6—F1 | 179.6 (3) |
N1—N2—C13—N4 | −1.2 (4) | C4—C5—C6—C1 | −0.6 (5) |
N1—C16—C17—C9 | 0.7 (4) | C6—C1—C2—C3 | 1.4 (5) |
N2—N1—C11—N3 | −179.6 (2) | C7—O1—C4—C3 | 176.9 (2) |
N2—N1—C11—N4 | 0.0 (3) | C7—O1—C4—C5 | −1.8 (4) |
N2—N1—C16—C17 | 179.0 (2) | C9—N3—C11—N1 | 0.9 (4) |
N3—C9—C17—C16 | 0.9 (4) | C9—N3—C11—N4 | −178.6 (3) |
C1—C2—C3—C4 | −0.1 (4) | C9—C3—C4—O1 | −2.1 (4) |
C1—C2—C3—C9 | −178.3 (3) | C9—C3—C4—C5 | 176.6 (3) |
C2—C1—C6—F1 | 178.7 (3) | C11—N1—N2—C13 | 0.7 (3) |
C2—C1—C6—C5 | −1.0 (5) | C11—N1—C16—C17 | −1.5 (4) |
C2—C3—C4—O1 | 179.8 (2) | C11—N3—C9—C3 | 179.7 (2) |
C2—C3—C4—C5 | −1.5 (4) | C11—N3—C9—C17 | −1.7 (4) |
C2—C3—C9—N3 | 37.3 (4) | C11—N4—C13—N2 | 1.2 (4) |
C2—C3—C9—C17 | −141.3 (3) | C13—N4—C11—N1 | −0.6 (3) |
C3—C4—C5—C6 | 1.9 (4) | C13—N4—C11—N3 | 179.0 (3) |
C3—C9—C17—C16 | 179.4 (2) | C16—N1—N2—C13 | −179.7 (3) |
C4—O1—C7—C8 | −179.5 (2) | C16—N1—C11—N3 | 0.7 (4) |
C4—C3—C9—N3 | −140.8 (3) | C16—N1—C11—N4 | −179.7 (2) |
C4—C3—C9—C17 | 40.6 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C5—H5···N4i | 0.93 | 2.60 | 3.492 (4) | 162 |
C16—H16···N2ii | 0.93 | 2.49 | 3.407 (4) | 168 |
C17—H17···O1 | 0.93 | 2.39 | 2.811 (3) | 107 |
Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) −x+3, −y+1, −z+2. |
Acknowledgements
The authors thank DST–PURSE, Mangalore University, Mangaluru, for providing the single-crystal X-ray diffraction facility. KSR thanks the DST, Indo-Korea (grant No. INT/Korea/dated/13/09/2011) and KBH thanks the UGC for providing a UGC meritorious fellowship.
References
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Gilandoust, M., Naveen, S., Harsha, K. B., Lokanath, N. K. & Rangappa, K. S. (2016). IUCrData, 1, x161712. Google Scholar
Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P., Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P. A. (2008). J. Appl. Cryst. 41, 466–470. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Mopper, K. & Zhou, X. (1990). Science, 250, 661–664. CrossRef CAS Web of Science Google Scholar
Rigaku (1999). NUMABS. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku (2011). CrystalClear SM Expert. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2015). Acta Cryst. C71, 3–8. Web of Science CrossRef IUCr Journals Google Scholar
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.