N-(3-Chloro-2-methyl­phen­yl)-6-oxo-1,6-di­hydro­pyridine-3-carboxamide

Tian, G.; Long, S.

doi:10.1107/S2414314623006028

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230602

https://doi.org/10.1107/S2414314623006028

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N-(3-Chloro-2-methylphenyl)-6-oxo-1,6-dihydropyridine-3-carboxamide

Guimiao Tian ^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 L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 23 May 2023; accepted 7 July 2023; online 14 July 2023)

In the crystal structure of the title compound, C₁₃H₁₁ClN₂O₂, the molecules form a three-dimensional network based on two types of hydrogen bonds between NH groups and the carbonyl oxygen atoms and amides. The molecule is highly twisted, as evidenced by the dihedral angle between the 6-oxo-1,6-dihydropyridine and benzene rings [88.1 (2)°].

Keywords: crystal structure; 6-oxo-1,6-dihydropyridine; N—H⋯O hydrogen bonds.

CCDC reference: 2280200

Structure description

The title compound (Fig. 1) is a structural isomer of N-phenyl-2-hydroxynicotinanilide, which has interesting structural properties (Liu et al., 2020 ; Zhoujin et al., 2021 ). We wondered if isomerization would lead to completely different synthons in the crystal structure. In our study, crystals were obtained by slowly evaporating a pyridine solution of the title compound. The molecule is highly twisted, as evidenced by the dihedral angle between the 6-oxo-1,6-dihydropyridine and benzene rings [88.1 (2)°]. In the crystal, the molecules form chains running in the a-axis direction through hydrogen bonds between NH groups and the carbonyl oxygen atoms of the amides (Fig. 2, Table 1). The 6-oxo-1,6-dihydropyridine rings form dimers through additional N—H⋯O hydrogen bonds.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	1.93	2.793 (3)	177
N2—H2⋯O2ⁱⁱ	0.86	2.08	2.926 (3)	166
Symmetry codes: (i) ; (ii) .

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

Figure 2
(a) Packing of the molecules in the title compound; (b) chain and dimer formation supported by intermolecular N–H⋯O=C hydrogen bonds (indicated by blue dashed lines).

Synthesis and crystallization

The title compound was synthesized with 6-oxo-1,6-dihydropyridine-3-carboxylic acid and 3-chloro-2-methylaniline as starting materials (Fig. 3). The pure sample was dissolved in bulk pyridine at 323 K, and the resulting solution was left in a refrigerator. Colorless block-shaped crystals (Fig. 4) were harvested after several days.

Figure 3
Synthesis of the title compound.

Figure 4
A representative crystal of the title compound.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₁ClN₂O₂
M_r	262.69
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	268
a, b, c (Å)	4.91237 (15), 10.3037 (3), 12.5876 (3)
α, β, γ (°)	105.890 (2), 96.422 (2), 99.361 (2)
V (Å³)	596.35 (3)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	2.81
Crystal size (mm)	0.11 × 0.05 × 0.04

Data collection
Diffractometer	Rigaku Oxford Diffraction, Synergy Custom system, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2021 )
T_min, T_max	0.482, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5870, 2362, 2023
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.633

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.184, 1.09
No. of reflections	2362
No. of parameters	164
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.47
Computer programs: CrysAlis PRO (Rigaku OD, 2021), SHELXT (Sheldrick, 2015a ), SHELXL (Sheldrick, 2015b ), OLEX2 (Dolomanov et al., 2009 ) and Mercury (Macrae et al., 2020 ).

Structural data

CCDC reference: 2280200

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314623006028/vm4061sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314623006028/vm4061Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314623006028/vm4061Isup3.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: SHELXL (Sheldrick, 2015b); molecular graphics: Olex2 (Dolomanov et al., 2009), Mercury (Macrae et al., 2020); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

N-(3-Chloro-2-methylphenyl)-6-oxo-1,6-dihydropyridine-3-carboxamide top

Crystal data top

C₁₃H₁₁ClN₂O₂	Z = 2
M_r = 262.69	F(000) = 272
Triclinic, P1	D_x = 1.463 Mg m⁻³
a = 4.91237 (15) Å	Cu Kα radiation, λ = 1.54184 Å
b = 10.3037 (3) Å	Cell parameters from 4316 reflections
c = 12.5876 (3) Å	θ = 3.7–77.4°
α = 105.890 (2)°	µ = 2.81 mm⁻¹
β = 96.422 (2)°	T = 268 K
γ = 99.361 (2)°	Block, clear light colourless
V = 596.35 (3) Å³	0.11 × 0.05 × 0.04 mm

Data collection top

Rigaku Oxford Diffraction, Synergy Custom system, HyPix diffractometer	2362 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	2023 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.059
Detector resolution: 10.0000 pixels mm^-1	θ_max = 77.6°, θ_min = 3.7°
ω scans	h = −6→6
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2021)	k = −12→12
T_min = 0.482, T_max = 1.000	l = −15→11
5870 measured reflections

Refinement top

Refinement on F²	Primary atom site location: dual
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.060	H-atom parameters constrained
wR(F²) = 0.184	w = 1/[σ²(F_o²) + (0.1286P)² + 0.0079P] where P = (F_o² + 2F_c²)/3
S = 1.09	(Δ/σ)_max < 0.001
2362 reflections	Δρ_max = 0.34 e Å⁻³
164 parameters	Δρ_min = −0.47 e Å⁻³
0 restraints

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. positions of H atoms at N1 and N2 were obtained from a difference Fourier map. Other H atoms were positioned geometrically with C—H = 0.93 Å (aromatic H) or 0.96 Å (methyl H), and constrained to ride on their parent atoms, with U_iso(H) = xU_eq(C,O), where x=1.5 for methyl H, and x=1.2 for all other H atoms.

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

	x	y	z	U_iso*/U_eq
Cl1	0.70169 (15)	0.48597 (7)	0.88602 (4)	0.0568 (3)
O1	0.2394 (4)	0.10879 (18)	−0.04783 (12)	0.0467 (4)
O2	1.0545 (3)	0.2472 (2)	0.40507 (14)	0.0554 (5)
N1	0.2702 (4)	0.07879 (18)	0.12455 (14)	0.0351 (4)
H1	0.113762	0.020388	0.103199	0.042*
N2	0.6373 (4)	0.23089 (19)	0.46700 (13)	0.0367 (4)
H2	0.459644	0.221023	0.448300	0.044*
C1	0.3982 (4)	0.1067 (2)	0.23115 (16)	0.0344 (5)
H1A	0.313595	0.064270	0.278844	0.041*
C2	0.6488 (4)	0.1959 (2)	0.27013 (16)	0.0327 (4)
C3	0.7723 (5)	0.2563 (2)	0.19387 (18)	0.0387 (5)
H3	0.946826	0.314972	0.217320	0.046*
C4	0.6407 (5)	0.2301 (2)	0.08749 (18)	0.0403 (5)
H4	0.724547	0.272452	0.039606	0.048*
C5	0.3741 (4)	0.1379 (2)	0.04762 (16)	0.0338 (5)
C6	0.7985 (4)	0.2265 (2)	0.38631 (17)	0.0357 (5)
C7	0.7463 (4)	0.2510 (2)	0.58157 (16)	0.0330 (5)
C8	0.6758 (4)	0.3534 (2)	0.66538 (16)	0.0312 (4)
C9	0.7869 (5)	0.3634 (2)	0.77585 (17)	0.0369 (5)
C10	0.9636 (5)	0.2817 (3)	0.80184 (19)	0.0436 (5)
H10	1.034339	0.292535	0.876128	0.052*
C11	1.0340 (6)	0.1845 (3)	0.7173 (2)	0.0498 (6)
H11	1.156189	0.129966	0.733910	0.060*
C12	0.9234 (6)	0.1669 (2)	0.6069 (2)	0.0465 (6)
H12	0.967423	0.098984	0.549550	0.056*
C13	0.4974 (5)	0.4497 (2)	0.64070 (18)	0.0413 (5)
H13A	0.614874	0.532952	0.638879	0.062*
H13B	0.384069	0.471175	0.697991	0.062*
H13C	0.378964	0.406824	0.569413	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0737 (5)	0.0721 (5)	0.0188 (4)	0.0169 (3)	0.0033 (3)	0.0046 (3)
O1	0.0527 (10)	0.0628 (10)	0.0219 (8)	0.0063 (7)	−0.0090 (7)	0.0172 (7)
O2	0.0327 (9)	0.1011 (14)	0.0257 (9)	0.0141 (8)	−0.0021 (6)	0.0103 (9)
N1	0.0348 (9)	0.0473 (9)	0.0185 (9)	0.0040 (7)	−0.0040 (6)	0.0080 (7)
N2	0.0337 (9)	0.0570 (10)	0.0151 (9)	0.0098 (7)	−0.0028 (6)	0.0060 (7)
C1	0.0374 (11)	0.0466 (10)	0.0172 (10)	0.0085 (8)	0.0000 (8)	0.0078 (8)
C2	0.0349 (10)	0.0440 (10)	0.0158 (9)	0.0105 (8)	−0.0012 (7)	0.0037 (8)
C3	0.0354 (11)	0.0483 (11)	0.0284 (11)	0.0051 (8)	0.0008 (8)	0.0087 (9)
C4	0.0455 (12)	0.0502 (11)	0.0258 (11)	0.0050 (9)	0.0024 (9)	0.0162 (9)
C5	0.0400 (11)	0.0406 (10)	0.0211 (10)	0.0116 (8)	−0.0009 (8)	0.0101 (8)
C6	0.0344 (11)	0.0491 (11)	0.0186 (10)	0.0098 (8)	−0.0036 (8)	0.0045 (8)
C7	0.0355 (10)	0.0430 (10)	0.0184 (10)	0.0052 (8)	−0.0026 (7)	0.0102 (8)
C8	0.0344 (10)	0.0409 (10)	0.0181 (10)	0.0031 (7)	0.0002 (7)	0.0125 (8)
C9	0.0455 (12)	0.0473 (11)	0.0155 (10)	0.0026 (8)	−0.0009 (8)	0.0116 (8)
C10	0.0500 (13)	0.0597 (13)	0.0229 (11)	0.0053 (10)	−0.0048 (9)	0.0227 (10)
C11	0.0577 (15)	0.0569 (13)	0.0415 (14)	0.0171 (11)	−0.0031 (11)	0.0269 (12)
C12	0.0582 (15)	0.0492 (12)	0.0333 (13)	0.0196 (10)	0.0010 (10)	0.0117 (10)
C13	0.0504 (13)	0.0490 (11)	0.0247 (11)	0.0157 (9)	−0.0013 (9)	0.0114 (9)

Geometric parameters (Å, º) top

Cl1—C9	1.743 (2)	C3—C4	1.355 (3)
O1—C5	1.238 (2)	C4—C5	1.434 (3)
O2—C6	1.225 (3)	C7—C8	1.391 (3)
N1—C1	1.349 (3)	C7—C12	1.394 (3)
N1—C5	1.379 (3)	C8—C9	1.406 (3)
N2—C6	1.351 (3)	C8—C13	1.497 (3)
N2—C7	1.427 (2)	C9—C10	1.376 (3)
C1—C2	1.360 (3)	C10—C11	1.366 (4)
C2—C3	1.418 (3)	C11—C12	1.387 (3)
C2—C6	1.487 (3)

C1—N1—C5	124.19 (18)	N2—C6—C2	116.39 (17)
C6—N2—C7	123.50 (17)	C8—C7—N2	119.96 (17)
N1—C1—C2	121.18 (19)	C8—C7—C12	121.34 (18)
C1—C2—C3	117.44 (18)	C12—C7—N2	118.70 (19)
C1—C2—C6	122.53 (18)	C7—C8—C9	116.00 (18)
C3—C2—C6	119.98 (18)	C7—C8—C13	122.62 (17)
C4—C3—C2	121.2 (2)	C9—C8—C13	121.36 (19)
C3—C4—C5	120.99 (19)	C8—C9—Cl1	118.95 (17)
O1—C5—N1	119.92 (19)	C10—C9—Cl1	117.88 (16)
O1—C5—C4	125.14 (19)	C10—C9—C8	123.2 (2)
N1—C5—C4	114.93 (17)	C11—C10—C9	119.3 (2)
O2—C6—N2	123.42 (19)	C10—C11—C12	120.1 (2)
O2—C6—C2	120.18 (19)	C11—C12—C7	120.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	1.93	2.793 (3)	177
N2—H2···O2ⁱⁱ	0.86	2.08	2.926 (3)	166

Symmetry codes: (i) −x, −y, −z; (ii) x−1, y, z.

References

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