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

Tu, N.; Long, S.

doi:10.1107/S241431462300603X

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 8| Part 7| July 2023| x230603

https://doi.org/10.1107/S241431462300603X

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

Ni Tu ^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 M. Weil, Vienna University of Technology, Austria (Received 16 May 2023; accepted 7 July 2023; online 14 July 2023)

Crystals of the title compound, C₁₂H₈Cl₂N₂O₂, were obtained by slow evaporation of an ethanolic solution. An intramolecular _amideN—H⋯O=C_lactam hydrogen bond is observed. In the crystal, two molecules pair up to form a centrosymmetric lactam–lactam dimers (LLD) by N—H⋯O=C hydrogen bonds, whereas the O=C_amide group of the molecule does not participate in hydrogen bonding.

Keywords: crystal structure; highly twisted conformation; lactam–lactam dimer; N—H⋯O hydrogen bonds.

CCDC reference: 2280201

Structure description

The molecule of the title compound has two main functional groups, i.e. an amide (C6, N2, O2) and a lactam (C1, N1, O1) moiety (Fig. 1). An intramolecular hydrogen bond is established between the amide NH group and the O atom of the lactam moiety (Fig. 2, Table 1). As a result of the large volume of the two chlorine substituents ortho to the C atom where the amide moiety is attached, the molecule has a twisted conformation with a dihedral angle between the two aromatic rings of 70.68 (13)°.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.01	2.703 (3)	137
N1—H1⋯O1ⁱ	0.82 (4)	1.97 (4)	2.794 (3)	175 (3)
Symmetry code: (i) .

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 crystal structure. N—H⋯O hydrogen bonds are indicated by dashed lines.

In the crystal structure, at least two synthons, i.e. a lactam–lactam dimer (LLD) and a lactam–amide catemer, are possible. In two previous studies, both synthons were observed due to different substitution patterns on the molecules (Liu et al., 2020 ; Zhoujin et al., 2021 ). In the crystal of the title compound, only the LLD synthon is observed in form of a centrosymmetric dimer established through _lactamN—H⋯O=C_lactam hydrogen bonds, whereas the O=C_amide group of the molecule does not participate in the formation of N—H⋯O hydrogen bonds (Table 1, Fig. 2).

Synthesis and crystallization

The title compound was synthesized in two steps with 2-hydroxynicotinic acid and 2,6-dichloroaniline as starting materials. First, 2-hydroxynicotinic acid was converted into 2-hydroxynicotinoyl chloride with thionyl chloride. Then 2-hydroxynicotinoyl chloride was reacted with 2,6-dichloroaniline to provide the title compound (Fig. 3). Single crystals of the title compound were obtained through slow evaporation of a saturated ethanolic solution. The details of the crystallization are as follows: about 30 mg of the compound was placed in a test tube, and an appropriate amount of solvent was added dropwise to dissolve the compound. The solution was filtered into a glass vial covered with a perforated parafilm (Hu et al., 2018 ). Slow evaporation of the solution led to colorless single crystals in about a week (Fig. 4).

Figure 3
Synthesis scheme to obtain (1).

Figure 4
A representative crystal of (1).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The H atom of the lactam moiety was refined freely.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₈Cl₂N₂O₂
M_r	283.10
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	297
a, b, c (Å)	7.3730 (6), 8.0091 (6), 10.8545 (6)
α, β, γ (°)	97.296 (6), 95.228 (6), 102.149 (7)
V (Å³)	616.93 (8)
Z	2
Radiation type	Cu Kα
μ (mm⁻¹)	4.71
Crystal size (mm)	0.21 × 0.18 × 0.17

Data collection
Diffractometer	XtaLAB Synergy R, DW system, HyPix
Absorption correction	Multi-scan (CrysAlis PRO; Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ )
T_min, T_max	0.140, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	5370, 2135, 1943
R_int	0.073
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.077, 0.210, 1.03
No. of reflections	2135
No. of parameters	168
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.74, −0.61
Computer programs: CrysAlis PRO (Rigaku OD, 2022 $[Rigaku OD (2022). CrysAlis PRO. Rigaku Oxford Diffraction, Tokyo, Japan.]$ ), SHELXT (Sheldrick, 2015a ), SHELXL Sheldrick, 2015b ), Mercury (Macrae et al., 2020 ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 2280201

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S241431462300603X/wm4188sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S241431462300603X/wm4188Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S241431462300603X/wm4188Isup3.cml

checkCIF report

Computing details top

Data collection: CrysAlis PRO (Rigaku OD, 2022); cell refinement: CrysAlis PRO (Rigaku OD, 2022); data reduction: CrysAlis PRO (Rigaku OD, 2022); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL Sheldrick, 2015b); molecular graphics: Mercury (Macrae et al., 2020); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

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

Crystal data top

C₁₂H₈Cl₂N₂O₂	Z = 2
M_r = 283.10	F(000) = 288
Triclinic, P1	D_x = 1.524 Mg m⁻³
a = 7.3730 (6) Å	Cu Kα radiation, λ = 1.54184 Å
b = 8.0091 (6) Å	Cell parameters from 4779 reflections
c = 10.8545 (6) Å	θ = 4.1–76.2°
α = 97.296 (6)°	µ = 4.71 mm⁻¹
β = 95.228 (6)°	T = 297 K
γ = 102.149 (7)°	Block, clear light colourless
V = 616.93 (8) Å³	0.21 × 0.18 × 0.17 mm

Data collection top

XtaLAB Synergy R, DW system, HyPix diffractometer	2135 independent reflections
Radiation source: Rotating-anode X-ray tube, Rigaku (Cu) X-ray Source	1943 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.073
Detector resolution: 10.0000 pixels mm^-1	θ_max = 66.6°, θ_min = 4.1°
ω scans	h = −8→8
Absorption correction: multi-scan (CrysAlisPro; Rigaku OD, 2022)	k = −9→8
T_min = 0.140, T_max = 1.000	l = −12→12
5370 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: mixed
Least-squares matrix: full	H atoms treated by a mixture of independent and constrained refinement
R[F² > 2σ(F²)] = 0.077	w = 1/[σ²(F_o²) + (0.173P)² + 0.0514P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.210	(Δ/σ)_max < 0.001
S = 1.03	Δρ_max = 0.74 e Å⁻³
2135 reflections	Δρ_min = −0.61 e Å⁻³
168 parameters	Extinction correction: SHELXL-2018/3 (Sheldrick 2015b), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.013 (4)
Primary atom site location: dual

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
Cl1	0.09456 (12)	0.25172 (11)	0.21934 (9)	0.0689 (4)
Cl2	0.33699 (11)	0.84435 (8)	0.03740 (7)	0.0606 (4)
O1	0.0726 (3)	0.8647 (3)	0.38156 (19)	0.0573 (6)
O2	0.4804 (3)	0.5753 (3)	0.32403 (18)	0.0601 (7)
N1	0.2015 (3)	0.9462 (3)	0.5833 (2)	0.0451 (6)
N2	0.2180 (3)	0.6370 (3)	0.2380 (2)	0.0449 (6)
H2	0.128318	0.688602	0.249405	0.054*
C1	0.1941 (3)	0.8550 (3)	0.4661 (2)	0.0416 (6)
C2	0.3370 (3)	0.7567 (3)	0.4535 (2)	0.0394 (6)
C3	0.4628 (4)	0.7595 (4)	0.5538 (3)	0.0458 (7)
H3	0.553867	0.695703	0.544571	0.055*
C4	0.4597 (4)	0.8558 (4)	0.6713 (3)	0.0498 (7)
H4	0.546583	0.856661	0.739168	0.060*
C5	0.3257 (4)	0.9469 (4)	0.6815 (3)	0.0478 (7)
H5	0.319516	1.011107	0.758020	0.057*
C6	0.3521 (4)	0.6494 (3)	0.3331 (2)	0.0414 (6)
C7	0.2203 (3)	0.5413 (3)	0.1196 (2)	0.0390 (6)
C8	0.1698 (3)	0.3609 (3)	0.0998 (3)	0.0441 (6)
C9	0.1746 (4)	0.2670 (4)	−0.0165 (3)	0.0533 (8)
H9	0.139775	0.146970	−0.028567	0.064*
C10	0.2312 (4)	0.3524 (4)	−0.1133 (3)	0.0542 (8)
H10	0.236139	0.289553	−0.190562	0.065*
C11	0.2804 (4)	0.5292 (4)	−0.0971 (3)	0.0484 (7)
H11	0.317890	0.586835	−0.162878	0.058*
C12	0.2733 (3)	0.6204 (3)	0.0189 (2)	0.0405 (6)
H1	0.118 (5)	0.999 (4)	0.589 (3)	0.047 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0707 (6)	0.0764 (6)	0.0693 (7)	0.0185 (4)	0.0188 (4)	0.0360 (5)
Cl2	0.0779 (6)	0.0474 (5)	0.0549 (6)	0.0110 (4)	0.0063 (4)	0.0078 (4)
O1	0.0613 (12)	0.0848 (15)	0.0359 (10)	0.0487 (11)	0.0014 (9)	−0.0050 (10)
O2	0.0628 (12)	0.0913 (15)	0.0394 (11)	0.0527 (11)	0.0088 (9)	−0.0018 (10)
N1	0.0521 (13)	0.0599 (13)	0.0319 (12)	0.0322 (10)	0.0106 (10)	0.0022 (10)
N2	0.0500 (12)	0.0643 (14)	0.0291 (12)	0.0346 (10)	0.0091 (9)	−0.0001 (10)
C1	0.0457 (13)	0.0540 (14)	0.0328 (13)	0.0253 (11)	0.0125 (11)	0.0055 (11)
C2	0.0446 (13)	0.0509 (14)	0.0308 (13)	0.0230 (10)	0.0130 (10)	0.0098 (11)
C3	0.0519 (14)	0.0557 (15)	0.0370 (14)	0.0278 (11)	0.0069 (11)	0.0063 (12)
C4	0.0600 (16)	0.0652 (17)	0.0310 (13)	0.0317 (13)	0.0034 (12)	0.0042 (12)
C5	0.0566 (15)	0.0610 (16)	0.0304 (13)	0.0234 (12)	0.0099 (11)	0.0032 (11)
C6	0.0472 (13)	0.0548 (14)	0.0311 (13)	0.0251 (10)	0.0142 (11)	0.0096 (11)
C7	0.0380 (12)	0.0509 (14)	0.0319 (13)	0.0213 (10)	0.0071 (10)	−0.0005 (11)
C8	0.0444 (13)	0.0512 (14)	0.0446 (15)	0.0223 (10)	0.0121 (11)	0.0119 (12)
C9	0.0537 (15)	0.0443 (13)	0.0626 (19)	0.0219 (11)	0.0054 (13)	−0.0062 (13)
C10	0.0576 (15)	0.0658 (17)	0.0430 (16)	0.0290 (13)	0.0135 (13)	−0.0082 (14)
C11	0.0531 (14)	0.0656 (17)	0.0315 (13)	0.0227 (12)	0.0139 (11)	0.0040 (12)
C12	0.0421 (12)	0.0461 (13)	0.0357 (13)	0.0158 (9)	0.0088 (10)	0.0029 (11)

Geometric parameters (Å, º) top

Cl1—C8	1.724 (3)	C3—C4	1.409 (4)
Cl2—C12	1.736 (3)	C4—H4	0.9300
O1—C1	1.244 (3)	C4—C5	1.350 (4)
O2—C6	1.223 (3)	C5—H5	0.9300
N1—C1	1.375 (4)	C7—C8	1.398 (4)
N1—C5	1.339 (4)	C7—C12	1.378 (4)
N1—H1	0.82 (4)	C8—C9	1.392 (4)
N2—H2	0.8600	C9—H9	0.9300
N2—C6	1.341 (3)	C9—C10	1.374 (5)
N2—C7	1.414 (3)	C10—H10	0.9300
C1—C2	1.448 (3)	C10—C11	1.369 (5)
C2—C3	1.359 (4)	C11—H11	0.9300
C2—C6	1.497 (3)	C11—C12	1.384 (4)
C3—H3	0.9300

C1—N1—H1	113 (2)	O2—C6—N2	122.4 (2)
C5—N1—C1	125.1 (2)	O2—C6—C2	120.6 (2)
C5—N1—H1	122 (2)	N2—C6—C2	117.0 (2)
C6—N2—H2	119.2	C8—C7—N2	121.1 (2)
C6—N2—C7	121.6 (2)	C12—C7—N2	122.0 (2)
C7—N2—H2	119.2	C12—C7—C8	116.9 (2)
O1—C1—N1	119.5 (2)	C7—C8—Cl1	119.9 (2)
O1—C1—C2	126.0 (2)	C9—C8—Cl1	119.1 (2)
N1—C1—C2	114.5 (2)	C9—C8—C7	121.0 (3)
C1—C2—C6	122.5 (2)	C8—C9—H9	120.2
C3—C2—C1	119.7 (2)	C10—C9—C8	119.7 (3)
C3—C2—C6	117.8 (2)	C10—C9—H9	120.2
C2—C3—H3	119.0	C9—C10—H10	119.6
C2—C3—C4	122.1 (2)	C11—C10—C9	120.7 (3)
C4—C3—H3	119.0	C11—C10—H10	119.6
C3—C4—H4	121.3	C10—C11—H11	120.6
C5—C4—C3	117.5 (3)	C10—C11—C12	118.8 (3)
C5—C4—H4	121.3	C12—C11—H11	120.6
N1—C5—C4	121.1 (3)	C7—C12—Cl2	119.05 (19)
N1—C5—H5	119.4	C7—C12—C11	122.9 (2)
C4—C5—H5	119.4	C11—C12—Cl2	118.0 (2)

Cl1—C8—C9—C10	178.9 (2)	C5—N1—C1—O1	−179.7 (3)
O1—C1—C2—C3	179.2 (3)	C5—N1—C1—C2	−0.9 (4)
O1—C1—C2—C6	−1.2 (4)	C6—N2—C7—C8	76.0 (3)
N1—C1—C2—C3	0.5 (4)	C6—N2—C7—C12	−103.5 (3)
N1—C1—C2—C6	−179.9 (2)	C6—C2—C3—C4	−179.7 (2)
N2—C7—C8—Cl1	2.5 (3)	C7—N2—C6—O2	−2.1 (4)
N2—C7—C8—C9	−179.1 (2)	C7—N2—C6—C2	178.9 (2)
N2—C7—C12—Cl2	−0.6 (3)	C7—C8—C9—C10	0.5 (4)
N2—C7—C12—C11	178.6 (2)	C8—C7—C12—Cl2	179.79 (17)
C1—N1—C5—C4	0.9 (5)	C8—C7—C12—C11	−1.0 (4)
C1—C2—C3—C4	−0.1 (4)	C8—C9—C10—C11	−0.9 (5)
C1—C2—C6—O2	176.1 (3)	C9—C10—C11—C12	0.4 (4)
C1—C2—C6—N2	−4.8 (4)	C10—C11—C12—Cl2	179.8 (2)
C2—C3—C4—C5	0.0 (5)	C10—C11—C12—C7	0.5 (4)
C3—C2—C6—O2	−4.3 (4)	C12—C7—C8—Cl1	−177.95 (18)
C3—C2—C6—N2	174.8 (2)	C12—C7—C8—C9	0.4 (4)
C3—C4—C5—N1	−0.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.01	2.703 (3)	137
N1—H1···O1ⁱ	0.82 (4)	1.97 (4)	2.794 (3)	175 (3)

Symmetry code: (i) −x, −y+2, −z+1.

References

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