5-(2-Eth­oxy-4-fluoro­phen­yl)-1,2,4-triazolo[1,5-a]pyrimidine

Gilandoust, M.; Harsha, K.B.; Madan Kumar, S.; Rakesh, K.S.; Lokanath, N.K.; Byrappa, K.; Rangappa, K.S.

doi:10.1107/S2414314616017703

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 11| November 2016| x161770

https://doi.org/10.1107/S2414314616017703

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5-(2-Ethoxy-4-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine

Maryam Gilandoust,^a K. B. Harsha,^a S. Madan Kumar,^b K. S. Rakesh,^a N. K. Lokanath,^c K. Byrappa ^d and K. S. Rangappa ^a ^*

^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

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 31 October 2016; accepted 7 November 2016; online 15 November 2016)

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 crystal structure 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.

Table 1
Hydrogen-bond geometry (Å, °)

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) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) -x+3, -y+1, -z+2.

Figure 1
A view of the title molecule, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level and the intramolecular hydrogen bond is shown as a dashed line.

The crystal structure features C—H⋯N hydrogen bonds (Fig. 2, 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.

Figure 2
A view along the a axis of the crystal packing of the title compound. Hydrogen bonds are drawn as dashed lines.

Synthesis 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 column chromatography using 60:120 mesh silica gel and EtOAc:hexane as eluent (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 refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₁FN₄O
M_r	258.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	3.9166 (3), 16.6608 (11), 18.8096 (14)
β (°)	93.232 (7)
V (Å³)	1225.44 (16)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.10
Crystal size (mm)	0.32 × 0.23 × 0.21

Data collection
Diffractometer	Rigaku Saturn724+
Absorption correction	Multi-scan (NUMABS; Rigaku, 1999 )
T_min, T_max	0.966, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	10165, 2171, 1458
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.182, 1.08
No. of reflections	2171
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.26
Computer programs: CrystalClear SM Expert (Rigaku, 2011 ), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), Mercury (Macrae et al., 2008 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1515262

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616017703/vm4017sup1.cif

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

checkCIF report

Computing details top

Data collection: CrystalClear SM Expert (Rigaku, 2011); cell refinement: 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).

5-(2-Ethoxy-4-fluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine top

Crystal data top

C₁₃H₁₁FN₄O	F(000) = 536
M_r = 258.26	D_x = 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

Data collection top

Rigaku Saturn724+ diffractometer	R_int = 0.059
profile data from ω–scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (NUMABS; Rigaku, 1999)	h = −4→3
T_min = 0.966, T_max = 0.979	k = −19→19
10165 measured reflections	l = −22→22
2171 independent reflections	2171 standard reflections
1458 reflections with I > 2σ(I)

Refinement top

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(F_o²) + (0.0817P)² + 0.3483P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.182	(Δ/σ)_max < 0.001
S = 1.08	Δρ_max = 0.24 e Å⁻³
2171 reflections	Δρ_min = −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

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

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