3-[5-(Pyridin-4-yl)-1,3,4-oxa­diazol-2-yl]-4H-chromen-4-one

Koh, D.

doi:10.1107/S2414314616016254

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 10| October 2016| x161625

https://doi.org/10.1107/S2414314616016254

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3-[5-(Pyridin-4-yl)-1,3,4-oxadiazol-2-yl]-4H-chromen-4-one

Dongsoo Koh ^a ^*

^aDepartment of Applied Chemistry, Dongduk Women's University, Seoul 136-714, Republic of Korea
^*Correspondence e-mail: dskoh@dongduk.ac.kr

Edited by K. Fejfarova, Institute of Biotechnology CAS, Czech Republic (Received 25 September 2016; accepted 13 October 2016; online 18 October 2016)

In the title molecule, C₁₆H₉N₃O₃, the plane of oxadiazole ring is almost coplanar with attached pyridine ring and chromenyl ring system, forming dihedral angles of 2.37 (3) and 6.71 (2)°, respectively. In the crystal, a pair of C—H⋯O and C—H⋯N hydrogen-bond interactions lead to the formation of dimers, which are linked together into [100] chains.

Keywords: crystal structure; oxadiazole; hydrogen bonding.

CCDC reference: 1509623

Structure description

Heterocycles possessing five-membered rings have attracted lots of interest due to their versatile pharmacological and biological activities. Oxadiazole is a furan-type five-membered ring heterocycle in which two nitrogen atoms substitute two carbons. Depending on the positions of the replacing nitrogen atoms, several types of oxadiazole isomers are formed. Examples of oxadiazole structures have been published (dos Santos et al., 2014 ; Sharma et al., 2014 ). In particular, 1,3,4-oxadiazoles have been extensively investigated in medicinal chemistry. They have been found to show anti-fungal (Wani et al. 2015 ), anti-inflammatory (Banerjee et al. 2015 ), anti-microbial (Li et al. 2015 ), and anticancer activities (Mochona et al. 2016 ).

We have focused our research on chalcones (Shin et al. 2014 , Lee et al. 2016 ), which have a central conjugated enone system connecting two aromatic rings. In a continuation of this research program, the central enone of chalcone was modified to an oxadiazole ring. Herein, the crystal structure of title oxadiazole compound is reported.

The molecular structure is shown in Fig. 1. The plane of the oxadiazole ring is almost co-planar with attached pyridine ring and chromenyl ring system, making dihedral angles of 2.37 (3) and 6.71 (2)°, respectively. In the crystal, a pair of C—H⋯O and C—H⋯N hydrogen bonds (Table 1) lead to the formation of dimers, which are linked together into [100] chains (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8⋯O1ⁱ	0.94	2.55	3.2517 (19)	132
C14—H14⋯N1ⁱ	0.94	2.63	3.248 (2)	123
Symmetry code: (i) x+1, y, z.

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level.

Figure 2
Part of the crystal structure of the title compound, showing the C—H⋯O and C—H⋯N hydrogen bonds as dashed lines. H atoms not involved in these interactions have been omitted for clarity.

Synthesis and crystallization

The synthetic procedure is shown in Fig. 3. To a solution of 4-oxo-4H-chromene-3-carbaldehyde (348 mg, 2 mmol) in 20 ml of anhydrous ethanol was added isonicotinohydrazide (274 mg, 2 mmol) and a catalytic amount of glacial acetic acid. The temperature of the mixture was adjusted to around 358 K in an oil-bath and the mixture was refluxed for 5 h. Then the reaction mixture was cooled down to the room temperature to give a precipitate. Filtration and washing with ethanol afforded a solid of the intermediate compound (I, 88%) which was used in the next step without further purification. The intermediate compound (I, 196 mg, 0.5 mmol) was dissolved in 10 ml of dichloromethane and iodobenzenediacetate (276 mg, 0.8 mmol) was added. The reaction mixture was stirred at room temperature for 12 h and the solvent was evaporated under vacuum to produce a solid. Recrystallization of the solid from methanol solution gave yellow block-shaped crystals for this study (m.p. 513–514 K).

Figure 3
The synthetic procedure for the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₆H₉N₃O₃
M_r	291.26
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	223
a, b, c (Å)	6.7439 (2), 10.8441 (3), 17.7415 (6)
β (°)	100.7317 (13)
V (Å³)	1274.77 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.13 × 0.12 × 0.09

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2000 )
T_min, T_max	0.986, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	38727, 3188, 2438
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.112, 1.07
No. of reflections	3188
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.19
Computer programs: APEX2 and SAINT (Bruker, 2000) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1509623

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016254/ff4010sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616016254/ff4010Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616016254/ff4010Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

3-[5-(Pyridin-4-yl)-1,3,4-oxadiazol-2-yl]-4H-chromen-4-one top

Crystal data top

C₁₆H₉N₃O₃	F(000) = 600
M_r = 291.26	D_x = 1.518 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9683 reflections
a = 6.7439 (2) Å	θ = 2.2–28.3°
b = 10.8441 (3) Å	µ = 0.11 mm⁻¹
c = 17.7415 (6) Å	T = 223 K
β = 100.7317 (13)°	Block, yellow
V = 1274.77 (7) Å³	0.13 × 0.12 × 0.09 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	3188 independent reflections
Radiation source: fine-focus sealed tube	2438 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
φ and ω scans	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −9→9
T_min = 0.986, T_max = 0.990	k = −14→14
38727 measured reflections	l = −23→23

Refinement top

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)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.112	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.045P)² + 0.5495P] where P = (F_o² + 2F_c²)/3
3188 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

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.

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.

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

	x	y	z	U_iso*/U_eq
C1	−0.1618 (2)	0.24444 (14)	0.01388 (8)	0.0301 (3)
O1	−0.31711 (18)	0.22005 (13)	0.03664 (8)	0.0540 (4)
C2	−0.1492 (2)	0.34564 (14)	−0.04011 (8)	0.0282 (3)
C3	−0.3161 (2)	0.42116 (15)	−0.06691 (9)	0.0361 (4)
H3	−0.4382	0.4078	−0.0498	0.043*
C4	−0.3024 (3)	0.51438 (16)	−0.11791 (10)	0.0421 (4)
H4	−0.4145	0.5652	−0.1353	0.050*
C5	−0.1229 (3)	0.53389 (16)	−0.14399 (10)	0.0417 (4)
H5	−0.1156	0.5972	−0.1796	0.050*
C6	0.0439 (3)	0.46201 (15)	−0.11854 (9)	0.0373 (4)
H6	0.1654	0.4756	−0.1360	0.045*
C7	0.0282 (2)	0.36883 (13)	−0.06637 (8)	0.0287 (3)
O2	0.19977 (16)	0.29944 (10)	−0.04199 (6)	0.0342 (3)
C8	0.1928 (2)	0.20816 (14)	0.00834 (9)	0.0299 (3)
H8	0.3118	0.1630	0.0251	0.036*
C9	0.0281 (2)	0.17627 (13)	0.03673 (8)	0.0254 (3)
C10	0.0427 (2)	0.07610 (13)	0.09176 (8)	0.0266 (3)
O3	0.21616 (14)	0.00778 (9)	0.10556 (5)	0.0247 (2)
C11	0.1816 (2)	−0.07098 (13)	0.16119 (8)	0.0265 (3)
N1	0.0061 (2)	−0.05671 (13)	0.17827 (9)	0.0408 (3)
N2	−0.0862 (2)	0.04037 (13)	0.13246 (9)	0.0411 (4)
C12	0.3365 (2)	−0.15833 (13)	0.19546 (8)	0.0257 (3)
C13	0.5241 (2)	−0.16371 (13)	0.17404 (8)	0.0285 (3)
H13	0.5565	−0.1107	0.1362	0.034*
C14	0.6622 (2)	−0.24943 (14)	0.21005 (9)	0.0319 (3)
H14	0.7887	−0.2532	0.1951	0.038*
N3	0.6283 (2)	−0.32645 (12)	0.26410 (8)	0.0350 (3)
C15	0.4466 (2)	−0.31961 (15)	0.28450 (9)	0.0363 (4)
H15	0.4194	−0.3732	0.3230	0.044*
C16	0.2980 (2)	−0.23835 (14)	0.25208 (9)	0.0320 (3)
H16	0.1727	−0.2371	0.2680	0.038*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0233 (7)	0.0345 (8)	0.0325 (7)	0.0026 (6)	0.0051 (6)	0.0007 (6)
O1	0.0276 (6)	0.0684 (9)	0.0695 (9)	0.0109 (6)	0.0183 (6)	0.0293 (7)
C2	0.0285 (7)	0.0289 (7)	0.0260 (7)	0.0024 (6)	0.0014 (5)	−0.0017 (6)
C3	0.0293 (8)	0.0385 (9)	0.0381 (8)	0.0055 (6)	0.0002 (6)	−0.0002 (7)
C4	0.0415 (9)	0.0385 (9)	0.0411 (9)	0.0092 (7)	−0.0056 (7)	0.0044 (7)
C5	0.0524 (10)	0.0362 (9)	0.0337 (8)	0.0030 (8)	0.0007 (7)	0.0089 (7)
C6	0.0413 (9)	0.0365 (8)	0.0343 (8)	−0.0002 (7)	0.0079 (7)	0.0042 (7)
C7	0.0295 (7)	0.0287 (7)	0.0268 (7)	0.0024 (6)	0.0027 (6)	−0.0012 (6)
O2	0.0285 (5)	0.0367 (6)	0.0390 (6)	0.0048 (4)	0.0109 (4)	0.0109 (5)
C8	0.0260 (7)	0.0306 (7)	0.0332 (7)	0.0042 (6)	0.0060 (6)	0.0041 (6)
C9	0.0243 (7)	0.0245 (7)	0.0269 (7)	0.0002 (5)	0.0036 (5)	−0.0011 (5)
C10	0.0219 (7)	0.0262 (7)	0.0318 (7)	0.0015 (5)	0.0057 (6)	−0.0016 (6)
O3	0.0234 (5)	0.0253 (5)	0.0257 (5)	0.0014 (4)	0.0050 (4)	0.0013 (4)
C11	0.0275 (7)	0.0241 (7)	0.0285 (7)	−0.0029 (5)	0.0066 (6)	0.0007 (6)
N1	0.0312 (7)	0.0402 (8)	0.0542 (9)	0.0060 (6)	0.0163 (6)	0.0192 (7)
N2	0.0323 (7)	0.0403 (8)	0.0543 (9)	0.0080 (6)	0.0171 (6)	0.0183 (7)
C12	0.0268 (7)	0.0235 (7)	0.0261 (7)	−0.0020 (5)	0.0027 (5)	−0.0020 (5)
C13	0.0290 (7)	0.0269 (7)	0.0305 (7)	−0.0017 (6)	0.0073 (6)	0.0013 (6)
C14	0.0261 (7)	0.0327 (8)	0.0367 (8)	−0.0013 (6)	0.0055 (6)	−0.0023 (6)
N3	0.0305 (7)	0.0331 (7)	0.0402 (7)	0.0027 (5)	0.0037 (6)	0.0049 (6)
C15	0.0360 (8)	0.0352 (8)	0.0377 (8)	0.0000 (7)	0.0071 (7)	0.0105 (7)
C16	0.0287 (8)	0.0327 (8)	0.0357 (8)	−0.0013 (6)	0.0088 (6)	0.0050 (6)

Geometric parameters (Å, º) top

C1—O1	1.2198 (19)	C9—C10	1.452 (2)
C1—C9	1.4687 (19)	C10—N2	1.2886 (19)
C1—C2	1.470 (2)	C10—O3	1.3677 (16)
C2—C7	1.385 (2)	O3—C11	1.3579 (16)
C2—C3	1.402 (2)	C11—N1	1.2844 (19)
C3—C4	1.371 (2)	C11—C12	1.4566 (19)
C3—H3	0.9400	N1—N2	1.4026 (19)
C4—C5	1.390 (3)	C12—C16	1.388 (2)
C4—H4	0.9400	C12—C13	1.389 (2)
C5—C6	1.374 (2)	C13—C14	1.385 (2)
C5—H5	0.9400	C13—H13	0.9400
C6—C7	1.388 (2)	C14—N3	1.323 (2)
C6—H6	0.9400	C14—H14	0.9400
C7—O2	1.3804 (17)	N3—C15	1.343 (2)
O2—C8	1.3398 (17)	C15—C16	1.377 (2)
C8—C9	1.347 (2)	C15—H15	0.9400
C8—H8	0.9400	C16—H16	0.9400

O1—C1—C9	123.91 (14)	C10—C9—C1	120.58 (12)
O1—C1—C2	122.36 (14)	N2—C10—O3	112.35 (13)
C9—C1—C2	113.73 (12)	N2—C10—C9	129.32 (13)
C7—C2—C3	117.99 (14)	O3—C10—C9	118.32 (12)
C7—C2—C1	120.88 (13)	C11—O3—C10	102.35 (11)
C3—C2—C1	121.13 (14)	N1—C11—O3	112.72 (13)
C4—C3—C2	120.38 (16)	N1—C11—C12	126.91 (13)
C4—C3—H3	119.8	O3—C11—C12	120.36 (12)
C2—C3—H3	119.8	C11—N1—N2	106.41 (12)
C3—C4—C5	120.12 (15)	C10—N2—N1	106.13 (12)
C3—C4—H4	119.9	C16—C12—C13	118.32 (13)
C5—C4—H4	119.9	C16—C12—C11	119.51 (13)
C6—C5—C4	120.97 (16)	C13—C12—C11	122.17 (13)
C6—C5—H5	119.5	C14—C13—C12	118.09 (13)
C4—C5—H5	119.5	C14—C13—H13	121.0
C5—C6—C7	118.22 (16)	C12—C13—H13	121.0
C5—C6—H6	120.9	N3—C14—C13	124.45 (14)
C7—C6—H6	120.9	N3—C14—H14	117.8
O2—C7—C2	121.44 (13)	C13—C14—H14	117.8
O2—C7—C6	116.25 (14)	C14—N3—C15	116.74 (13)
C2—C7—C6	122.30 (14)	N3—C15—C16	123.53 (14)
C8—O2—C7	118.70 (12)	N3—C15—H15	118.2
O2—C8—C9	124.91 (13)	C16—C15—H15	118.2
O2—C8—H8	117.5	C15—C16—C12	118.86 (14)
C9—C8—H8	117.5	C15—C16—H16	120.6
C8—C9—C10	119.08 (13)	C12—C16—H16	120.6
C8—C9—C1	120.32 (13)

O1—C1—C2—C7	−178.30 (15)	C1—C9—C10—N2	−7.4 (2)
C9—C1—C2—C7	1.2 (2)	C8—C9—C10—O3	−8.0 (2)
O1—C1—C2—C3	1.4 (2)	C1—C9—C10—O3	173.75 (12)
C9—C1—C2—C3	−179.09 (13)	N2—C10—O3—C11	−2.00 (16)
C7—C2—C3—C4	0.4 (2)	C9—C10—O3—C11	177.07 (12)
C1—C2—C3—C4	−179.31 (14)	C10—O3—C11—N1	1.97 (16)
C2—C3—C4—C5	0.6 (3)	C10—O3—C11—C12	−177.28 (12)
C3—C4—C5—C6	−1.0 (3)	O3—C11—N1—N2	−1.26 (18)
C4—C5—C6—C7	0.4 (3)	C12—C11—N1—N2	177.93 (14)
C3—C2—C7—O2	179.26 (13)	O3—C10—N2—N1	1.33 (18)
C1—C2—C7—O2	−1.1 (2)	C9—C10—N2—N1	−177.61 (14)
C3—C2—C7—C6	−1.0 (2)	C11—N1—N2—C10	−0.05 (18)
C1—C2—C7—C6	178.66 (14)	N1—C11—C12—C16	1.1 (2)
C5—C6—C7—O2	−179.60 (14)	O3—C11—C12—C16	−179.80 (13)
C5—C6—C7—C2	0.7 (2)	N1—C11—C12—C13	−178.16 (15)
C2—C7—O2—C8	−0.2 (2)	O3—C11—C12—C13	1.0 (2)
C6—C7—O2—C8	−179.93 (13)	C16—C12—C13—C14	0.5 (2)
C7—O2—C8—C9	1.3 (2)	C11—C12—C13—C14	179.71 (13)
O2—C8—C9—C10	−179.26 (13)	C12—C13—C14—N3	−0.5 (2)
O2—C8—C9—C1	−1.0 (2)	C13—C14—N3—C15	0.1 (2)
O1—C1—C9—C8	179.27 (16)	C14—N3—C15—C16	0.3 (2)
C2—C1—C9—C8	−0.3 (2)	N3—C15—C16—C12	−0.3 (2)
O1—C1—C9—C10	−2.5 (2)	C13—C12—C16—C15	−0.1 (2)
C2—C1—C9—C10	177.96 (12)	C11—C12—C16—C15	−179.37 (14)
C8—C9—C10—N2	170.89 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8···O1ⁱ	0.94	2.55	3.2517 (19)	132
C14—H14···N1ⁱ	0.94	2.63	3.248 (2)	123

Symmetry code: (i) x+1, y, z.

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