4-Oxo-N-phenyl-1,4-di­hydro­pyridine-3-carboxamide

Shu, X.; Long, S.

doi:10.1107/S2414314623006016

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230601

https://doi.org/10.1107/S2414314623006016

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4-Oxo-N-phenyl-1,4-dihydropyridine-3-carboxamide

Xi Shu ^a and Sihui Long ^a ^*

^aSchool of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan, Hubei 430205, People's Republic of China
^*Correspondence e-mail: sihuilong@wit.edu.cn

Edited by W. Imhof, University Koblenz-Landau, Germany (Received 16 May 2023; accepted 7 July 2023; online 14 July 2023)

The title compound, C₁₂H₁₀N₂O₂, shows a nearly planar conformation. The crystal structure is sustained by hydrogen bonds between the NH and the carbonyl O function of the 4-oxo-1,4-dihydropyridine ring of the molecules, forming infinite chains along the b-axis direction.

Keywords: crystal structure; hydrogen bonding.

CCDC reference: 2280191

Structure description

The title compound (Fig. 1) is a derivative of N-phenylnicotinamide, which is an efficient molluscicide (Dunlop et al., 1980 ). In addition, the compound can be used as a raw material for many chemical reactions. We were interested in its solid-state behavior since it is a structural isomer of N-phenyl-2-hydroxynicotinanilide, which has interesting structural properties (Zhoujin et al., 2021 ). In our study, the compound was synthesized by an amide condensation reaction (Narajan et al., 2016 ), and single crystals were obtained by slow evaporation of an acetone solution of the compound. The compound has a nearly planar conformation as evidenced by the dihedral angle between the 4-oxo-1,4-dihydropyridine and benzene rings of 6.80 (8)°. An intramolecular hydrogen bond is formed between the NH of the amide and the carbonyl O atom on the 4-oxo-1,4-dihydropyridine ring. In the crystal, the molecules form chains along the b-axis direction through hydrogen bonds between the NH group and the carbonyl O atom of the 4-oxo-1,4-dihydropyridine ring (Fig. 2, Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.91 (2)	1.84 (3)	2.744 (2)	171 (2)
C8—H8⋯O2	0.93	2.27	2.861 (2)	121
N2—H2⋯O1	0.88 (3)	1.91 (2)	2.6731 (18)	144 (2)
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Figure 1
Molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level.

Figure 2
Packing of the molecules in the title compound viewed along the b axis.

Synthesis and crystallization

4-Hydroxynicotinic acid (0.51 g, 3.67 mmol), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC, 1.06 g, 5.51 mmol) and hydroxybenzotriazole (HOBT, 0.60 g, 4.40 mmol) were dissolved in 6 ml of DMF and stirred at 0°C for 1 h. Then diisopropylethylamine (DIPEA, 0.95 g, 7.34 mmol) and aniline (0.28 ml, 3.67 mmol) were added and the reaction was completed under continuous stirring at 50°C for 12 h. Then 20 ml of deionized water were added to the reaction mixture, which was placed into a refrigerator at 5°C overnight. The resulting precipitate was collected by filtration and washed with deionized water to obtain 0.306 g (39% based on 4-hydroxynicotinic acid) of the title compound (Fig. 3). The obtained compound was fully dissolved in acetone under ultrasound until a clear solution was obtained, which was then filtered into a transparent glass bottle. The bottle was placed in a fume hood for slow evaporation of the solvent. Colorless rod-shaped crystals (Fig. 4) were obtained in a few days.

Figure 3
Reaction scheme.

Figure 4
A representative crystal of 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	C₁₂H₁₀N₂O₂
M_r	214.22
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	276
a, b, c (Å)	6.68228 (10), 11.79159 (18), 13.1717 (2)
V (Å³)	1037.86 (3)
Z	4
Radiation type	Cu Kα
μ (mm⁻¹)	0.79
Crystal size (mm)	0.1 × 0.07 × 0.05

Data collection
Diffractometer	Rigaku Oxford Diffraction, Synergy Custom system, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ )
T_min, T_max	0.864, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	6101, 2075, 2003
R_int	0.019
(sin θ/λ)_max (Å⁻¹)	0.632

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.083, 1.06
No. of reflections	2075
No. of parameters	154
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.14
Absolute structure	Flack x determined using 788 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	0.11 (8)
Computer programs: CrysAlis PRO (Rigaku OD, 2021 $[Rigaku OD (2021). CrysAlis PRO. Rigaku Oxford Diffraction, Yarnton, England.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL2018/3 (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2020 ).

Structural data

CCDC reference: 2280191

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314623006016/im4020sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006016/im4020Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006016/im4020Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO 1.171.41.113a (Rigaku OD, 2021); cell refinement: CrysAlis PRO 1.171.41.113a (Rigaku OD, 2021); data reduction: CrysAlis PRO 1.171.41.113a (Rigaku OD, 2021); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2018/3 (Sheldrick, 2015b); molecular graphics: Olex2 1.5 (Dolomanov et al., 2009), Mercury (Macrae et al., 2020); software used to prepare material for publication: Olex2 1.5 (Dolomanov et al., 2009).

4-Oxo-N-phenyl-1,4-dihydropyridine-3-carboxamide top

Crystal data top

C₁₂H₁₀N₂O₂	D_x = 1.371 Mg m⁻³
M_r = 214.22	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 5537 reflections
a = 6.68228 (10) Å	θ = 3.3–77.1°
b = 11.79159 (18) Å	µ = 0.79 mm⁻¹
c = 13.1717 (2) Å	T = 276 K
V = 1037.86 (3) Å³	Block, clear light colourless
Z = 4	0.1 × 0.07 × 0.05 mm
F(000) = 448

Data collection top

Rigaku Oxford Diffraction, Synergy Custom system, HyPix diffractometer	2075 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	2003 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.019
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.2°, θ_min = 5.0°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −13→14
T_min = 0.864, T_max = 1.000	l = −14→16
6101 measured reflections

Refinement top

Refinement on F²	H atoms treated by a mixture of independent and constrained refinement
Least-squares matrix: full	w = 1/[σ²(F_o²) + (0.0478P)² + 0.0929P] where P = (F_o² + 2F_c²)/3
R[F² > 2σ(F²)] = 0.030	(Δ/σ)_max < 0.001
wR(F²) = 0.083	Δρ_max = 0.21 e Å⁻³
S = 1.06	Δρ_min = −0.14 e Å⁻³
2075 reflections	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
154 parameters	Extinction coefficient: 0.027 (3)
0 restraints	Absolute structure: Flack x determined using 788 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
Primary atom site location: dual	Absolute structure parameter: 0.11 (8)
Hydrogen site location: mixed

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. The positions of H atoms at N1 and N2 were obtained from the difference Fourier map and were refined freely. Other H atoms were positioned geometrically with C—H = 0.93 Å and constrained to ride on their parent atoms, with U_iso(H) = 1.2 U_eq(C) (Table 2).

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

	x	y	z	U_iso*/U_eq
O1	0.25139 (19)	0.41568 (10)	0.25242 (11)	0.0504 (4)
O2	0.4568 (3)	0.68655 (14)	0.4334 (2)	0.0985 (8)
N1	−0.0559 (2)	0.71242 (14)	0.26837 (14)	0.0522 (4)
H1	−0.122 (4)	0.780 (2)	0.2688 (18)	0.060 (6)*
N2	0.5233 (2)	0.50907 (12)	0.37556 (12)	0.0418 (3)
C1	0.1596 (3)	0.50951 (14)	0.25749 (13)	0.0415 (4)
C2	0.2281 (3)	0.60428 (14)	0.31705 (14)	0.0417 (4)
C3	0.1157 (3)	0.70093 (15)	0.32024 (16)	0.0497 (4)
H3	0.159842	0.761165	0.359932	0.060*
C4	−0.1229 (3)	0.62714 (18)	0.20986 (16)	0.0553 (5)
H4	−0.240686	0.636483	0.173182	0.066*
C5	−0.0226 (3)	0.52847 (17)	0.20341 (15)	0.0534 (5)
H5	−0.073310	0.470945	0.162547	0.064*
C6	0.4136 (3)	0.60500 (15)	0.38116 (17)	0.0485 (5)
C7	0.7012 (2)	0.48310 (14)	0.42740 (12)	0.0372 (4)
C8	0.8102 (3)	0.56149 (14)	0.48339 (13)	0.0414 (4)
H8	0.766564	0.636194	0.488177	0.050*
C9	0.9846 (3)	0.52788 (17)	0.53218 (15)	0.0489 (4)
H9	1.056878	0.580418	0.569958	0.059*
C10	1.0519 (3)	0.41749 (18)	0.52534 (16)	0.0534 (5)
H10	1.168367	0.395585	0.558657	0.064*
C11	0.9447 (3)	0.33961 (16)	0.46848 (15)	0.0512 (5)
H11	0.989888	0.265248	0.463118	0.061*
C12	0.7708 (3)	0.37210 (15)	0.41965 (14)	0.0447 (4)
H12	0.699818	0.319469	0.381348	0.054*
H2	0.471 (3)	0.455 (2)	0.3385 (19)	0.061 (7)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0506 (7)	0.0403 (6)	0.0602 (8)	−0.0014 (5)	−0.0053 (6)	−0.0110 (5)
O2	0.0752 (11)	0.0582 (10)	0.162 (2)	0.0273 (8)	−0.0592 (12)	−0.0567 (11)
N1	0.0498 (8)	0.0454 (8)	0.0614 (10)	0.0053 (7)	−0.0058 (7)	0.0124 (7)
N2	0.0383 (7)	0.0354 (7)	0.0518 (8)	−0.0002 (6)	−0.0030 (6)	−0.0095 (6)
C1	0.0434 (8)	0.0399 (8)	0.0411 (8)	−0.0060 (7)	0.0023 (7)	0.0022 (7)
C2	0.0404 (8)	0.0369 (8)	0.0478 (9)	−0.0013 (6)	0.0012 (7)	0.0006 (7)
C3	0.0482 (9)	0.0395 (9)	0.0613 (11)	0.0018 (7)	−0.0056 (8)	0.0019 (8)
C4	0.0516 (10)	0.0588 (11)	0.0555 (11)	−0.0042 (9)	−0.0138 (9)	0.0172 (9)
C5	0.0586 (11)	0.0510 (10)	0.0506 (10)	−0.0091 (9)	−0.0146 (9)	0.0035 (8)
C6	0.0429 (9)	0.0349 (8)	0.0677 (12)	0.0013 (7)	−0.0071 (8)	−0.0117 (8)
C7	0.0363 (7)	0.0371 (8)	0.0383 (7)	−0.0004 (6)	0.0048 (6)	−0.0016 (6)
C8	0.0422 (8)	0.0374 (8)	0.0445 (9)	−0.0024 (6)	0.0020 (7)	−0.0028 (7)
C9	0.0469 (9)	0.0532 (10)	0.0465 (9)	−0.0069 (8)	−0.0044 (8)	−0.0033 (8)
C10	0.0470 (9)	0.0621 (11)	0.0510 (10)	0.0061 (8)	−0.0060 (8)	0.0042 (9)
C11	0.0550 (10)	0.0451 (9)	0.0536 (11)	0.0116 (8)	0.0016 (9)	−0.0004 (8)
C12	0.0483 (9)	0.0376 (8)	0.0482 (9)	0.0002 (7)	−0.0003 (8)	−0.0051 (7)

Geometric parameters (Å, º) top

O1—C1	1.267 (2)	C4—C5	1.346 (3)
O2—C6	1.217 (2)	C5—H5	0.9300
N1—H1	0.91 (2)	C7—C8	1.389 (2)
N1—C3	1.341 (3)	C7—C12	1.393 (2)
N1—C4	1.344 (3)	C8—H8	0.9300
N2—C6	1.350 (2)	C8—C9	1.388 (2)
N2—C7	1.405 (2)	C9—H9	0.9300
N2—H2	0.88 (3)	C9—C10	1.380 (3)
C1—C2	1.440 (2)	C10—H10	0.9300
C1—C5	1.428 (2)	C10—C11	1.384 (3)
C2—C3	1.365 (2)	C11—H11	0.9300
C2—C6	1.500 (2)	C11—C12	1.382 (3)
C3—H3	0.9300	C12—H12	0.9300
C4—H4	0.9300

C3—N1—H1	120.0 (15)	O2—C6—N2	124.36 (17)
C3—N1—C4	120.09 (17)	O2—C6—C2	121.23 (16)
C4—N1—H1	119.8 (15)	N2—C6—C2	114.41 (15)
C6—N2—C7	128.00 (15)	C8—C7—N2	123.83 (15)
C6—N2—H2	115.0 (16)	C8—C7—C12	119.29 (15)
C7—N2—H2	116.8 (16)	C12—C7—N2	116.87 (15)
O1—C1—C2	123.54 (16)	C7—C8—H8	120.1
O1—C1—C5	121.55 (16)	C9—C8—C7	119.73 (16)
C5—C1—C2	114.91 (16)	C9—C8—H8	120.1
C1—C2—C6	125.01 (15)	C8—C9—H9	119.6
C3—C2—C1	119.31 (16)	C10—C9—C8	120.84 (17)
C3—C2—C6	115.63 (15)	C10—C9—H9	119.6
N1—C3—C2	122.60 (17)	C9—C10—H10	120.3
N1—C3—H3	118.7	C9—C10—C11	119.48 (17)
C2—C3—H3	118.7	C11—C10—H10	120.3
N1—C4—H4	119.4	C10—C11—H11	119.9
N1—C4—C5	121.13 (17)	C12—C11—C10	120.18 (18)
C5—C4—H4	119.4	C12—C11—H11	119.9
C1—C5—H5	119.0	C7—C12—H12	119.8
C4—C5—C1	121.92 (17)	C11—C12—C7	120.47 (17)
C4—C5—H5	119.0	C11—C12—H12	119.8

O1—C1—C2—C3	−178.02 (16)	C5—C1—C2—C3	1.9 (3)
O1—C1—C2—C6	−0.6 (3)	C5—C1—C2—C6	179.37 (17)
O1—C1—C5—C4	178.76 (18)	C6—N2—C7—C8	−9.9 (3)
N1—C4—C5—C1	−0.4 (3)	C6—N2—C7—C12	171.15 (18)
N2—C7—C8—C9	179.95 (16)	C6—C2—C3—N1	−178.90 (18)
N2—C7—C12—C11	−179.93 (16)	C7—N2—C6—O2	0.9 (4)
C1—C2—C3—N1	−1.2 (3)	C7—N2—C6—C2	−178.75 (16)
C1—C2—C6—O2	−176.4 (2)	C7—C8—C9—C10	0.4 (3)
C1—C2—C6—N2	3.3 (3)	C8—C7—C12—C11	1.1 (3)
C2—C1—C5—C4	−1.2 (3)	C8—C9—C10—C11	0.4 (3)
C3—N1—C4—C5	1.2 (3)	C9—C10—C11—C12	−0.5 (3)
C3—C2—C6—O2	1.2 (3)	C10—C11—C12—C7	−0.3 (3)
C3—C2—C6—N2	−179.15 (17)	C12—C7—C8—C9	−1.1 (2)
C4—N1—C3—C2	−0.4 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.91 (2)	1.84 (3)	2.744 (2)	171 (2)
C8—H8···O2	0.93	2.27	2.861 (2)	121
N2—H2···O1	0.88 (3)	1.91 (2)	2.6731 (18)	144 (2)

Symmetry code: (i) −x, y+1/2, −z+1/2.

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