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

Abstract

The title compound, C₁₃H₁₁BrN₂O₂, consists of two six-membered rings linked by an amide group and adopts a near planar conformation. The dihedral angle between the two rings is 8.38 (11)°. In the crystal structure, there are intra- and inter­molecular N—H⋯O hydrogen bonds, the latter forming inversion dimers.

Related literature  

For a related structure, see: Long et al. (2006 ▶). For background and details of synthesis, see: Ting et al. (1990 ▶).

Experimental  

Crystal data  

• C₁₃H₁₁BrN₂O₂

• M _r = 307.15

• Triclinic,

• a = 7.164 (1) Å

• b = 7.715 (1) Å

• c = 10.446 (2) Å

• α = 88.23 (1)°

• β = 89.18 (1)°

• γ = 89.68 (1)°

• V = 577.01 (16) ų

• Z = 2

• Mo Kα radiation

• μ = 3.56 mm⁻¹

• T = 90 K

• 0.30 × 0.10 × 0.04 mm

Data collection  

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.415, T _max = 0.871

• 5027 measured reflections

• 2637 independent reflections

• 2273 reflections with I > 2σ(I)

• R _int = 0.032

Refinement  

• R[F ² > 2σ(F ²)] = 0.031

• wR(F ²) = 0.072

• S = 1.07

• 2637 reflections

• 164 parameters

• H-atom parameters constrained

• Δρ_max = 0.94 e Å⁻³

• Δρ_min = −0.61 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: DENZO-SMN (Otwinowski & Minor, 1997 ▶); data reduction: DENZO-SMN; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812011294/ff2058Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2	0.88	1.90	2.660 (3)	144
N2—H2A⋯O2i	0.88	1.91	2.785 (3)	171

Symmetry code: (i) .

supplementary crystallographic information

Comment

The title compound (I) was obtained as a by-product during an effort to make 2-(2-methyl-3-bromoanilino)nicotinic acid by reacting 2-chloronicotinic acid with 3-bromo-2-methylaniline through a modified procedure from Ting et al. (1990). Similar to the case of N-(3-chloro-2-methylphenyl)-1,2-dihydro-2-oxo-3 -pyridinecarboxamide (Long et al., 2006), the crystal structure analysis revealed it is the keto-amine (or lactam) tautomer, rather than the hydroxy-pyridine tautomer (II) (Fig. 1, Table 1). The two aromatic rings of the molecule are linked by an amide group. Due to the extended π-conjugation system throughout the whole molecule via the amide bridge, the molecule takes a near planar conformation. The dihedral angle between the two aromatic rings is 8.38 (11)°.

Centrosymmetric dimers are formed through intra- and intermolecular N—H···O hydrogen bonds (Table 2). Essentially, the title compound is isostructural with N-(3-chloro-2-methylphenyl)-1,2-dihydro-2-oxo-3-pyridinecarboxamide, since the only difference is bromine in the title compound and chlorine in the counterpart.

Experimental

2-Chloronicotinic acid (1.9 g, 12.1 mmol), 3-bromo-2-methyl-aniline (2.5 g, 13.4 mmol), and pyridine (1.0 ml, 12 mmol) were added to a round-bottom flask, followed by introduction of p-toluenesulfonic acid (0.3 g, 1.8 mmol) in 10 ml of water. The resulted solution was refluxed overnight. Colorless solid precipitated out after the mixture was cooled down to room temperature, and it was characterized by NMR to be the title compound (I). Crystals were grown from MeOH solution by slow evaporation.

Refinement

H atoms were located in difference Fourier maps and subsequently placed in idealized positions with constrained C—H distances of 0.95 (C_Ar—H), 0.98 (C_Me—H) and 0.88 Å (N—H). U_iso(H) values were set to 1.2U_eq(C,N) or 1.5U_eq(C) for methyl group.

Figures

Fig. 1.

The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level (arbitrary spheres for the H atoms).

Fig. 2.

Tautomerism of the title compound.

Crystal data

C13H11BrN2O2	Z = 2
Mr = 307.15	F(000) = 308
Triclinic, P1	Dx = 1.768 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.164 (1) Å	Cell parameters from 2552 reflections
b = 7.715 (1) Å	θ = 1.0–27.5°
c = 10.446 (2) Å	µ = 3.56 mm−1
α = 88.23 (1)°	T = 90 K
β = 89.18 (1)°	Thick plate, colourless
γ = 89.68 (1)°	0.30 × 0.10 × 0.04 mm
V = 577.01 (16) Å3

Data collection

Nonius KappaCCD diffractometer	2637 independent reflections
Radiation source: fine-focus sealed tube	2273 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
Detector resolution: 18 pixels mm-1	θmax = 27.5°, θmin = 2.0°
ω scans at fixed χ = 55°	h = −9→9
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	k = −10→10
Tmin = 0.415, Tmax = 0.871	l = −13→13
5027 measured reflections

Refinement

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.072	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0231P)2 + 0.5699P] where P = (Fo2 + 2Fc2)/3
2637 reflections	(Δ/σ)max = 0.001
164 parameters	Δρmax = 0.94 e Å−3
0 restraints	Δρmin = −0.61 e Å−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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 > σ(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 (Ų)

	x	y	z	Uiso*/Ueq
C1	0.1649 (3)	0.2509 (3)	0.8354 (2)	0.0184 (5)
C2	0.1129 (3)	0.0867 (3)	0.7987 (3)	0.0194 (5)
H2	0.0843	−0.0021	0.8608	0.023*
C3	0.1039 (3)	0.0564 (3)	0.6692 (3)	0.0201 (5)
H3	0.0677	−0.0547	0.6421	0.024*
C4	0.1469 (3)	0.1848 (3)	0.5786 (2)	0.0179 (5)
H4	0.1410	0.1614	0.4900	0.021*
C5	0.1990 (3)	0.3492 (3)	0.6174 (2)	0.0170 (5)
C6	0.2097 (3)	0.3859 (3)	0.7489 (2)	0.0160 (5)
C7	0.2664 (4)	0.5641 (3)	0.7890 (2)	0.0193 (5)
H7A	0.2662	0.5674	0.8827	0.029*
H7B	0.1780	0.6505	0.7548	0.029*
H7C	0.3920	0.5900	0.7555	0.029*
C8	0.2416 (3)	0.4880 (3)	0.3990 (2)	0.0176 (5)
C9	0.3033 (3)	0.6573 (3)	0.3379 (2)	0.0161 (5)
C10	0.2884 (3)	0.6775 (3)	0.2073 (2)	0.0189 (5)
H10	0.2405	0.5845	0.1603	0.023*
C11	0.3414 (4)	0.8303 (3)	0.1408 (2)	0.0213 (6)
H11	0.3299	0.8417	0.0505	0.026*
C12	0.4098 (4)	0.9616 (4)	0.2098 (2)	0.0199 (5)
H12	0.4471	1.0668	0.1674	0.024*
C13	0.3763 (3)	0.7979 (3)	0.4092 (2)	0.0160 (5)
N1	0.2464 (3)	0.4838 (3)	0.52988 (19)	0.0163 (4)
H1	0.2850	0.5797	0.5642	0.020*
N2	0.4252 (3)	0.9437 (3)	0.3384 (2)	0.0174 (4)
H2A	0.4699	1.0318	0.3796	0.021*
O1	0.1914 (3)	0.3676 (2)	0.33371 (17)	0.0226 (4)
O2	0.3985 (2)	0.7976 (2)	0.52859 (16)	0.0190 (4)
Br1	0.17131 (4)	0.28503 (3)	1.01565 (2)	0.02315 (10)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
C1	0.0152 (13)	0.0185 (13)	0.0217 (13)	0.0025 (10)	−0.0020 (10)	−0.0010 (10)
C2	0.0146 (13)	0.0158 (12)	0.0275 (13)	0.0003 (10)	−0.0007 (10)	0.0019 (10)
C3	0.0145 (13)	0.0144 (12)	0.0316 (14)	−0.0011 (10)	−0.0022 (11)	−0.0040 (11)
C4	0.0142 (12)	0.0184 (12)	0.0214 (13)	−0.0003 (10)	−0.0024 (10)	−0.0048 (10)
C5	0.0103 (12)	0.0172 (12)	0.0234 (13)	0.0008 (9)	−0.0019 (10)	−0.0012 (10)
C6	0.0099 (12)	0.0162 (12)	0.0220 (12)	0.0017 (9)	−0.0008 (10)	−0.0035 (10)
C7	0.0238 (14)	0.0165 (12)	0.0178 (12)	−0.0005 (10)	0.0017 (10)	−0.0026 (10)
C8	0.0120 (12)	0.0189 (12)	0.0223 (13)	0.0025 (10)	−0.0013 (10)	−0.0046 (10)
C9	0.0113 (12)	0.0186 (12)	0.0185 (12)	0.0018 (9)	−0.0005 (9)	−0.0021 (10)
C10	0.0149 (13)	0.0224 (13)	0.0198 (12)	0.0006 (10)	−0.0025 (10)	−0.0055 (10)
C11	0.0186 (13)	0.0275 (14)	0.0177 (12)	0.0031 (11)	−0.0024 (10)	−0.0001 (11)
C12	0.0159 (13)	0.0248 (14)	0.0187 (12)	0.0001 (10)	0.0004 (10)	0.0037 (10)
C13	0.0120 (12)	0.0174 (12)	0.0186 (12)	0.0026 (9)	0.0008 (9)	−0.0025 (10)
N1	0.0179 (11)	0.0150 (10)	0.0163 (10)	−0.0017 (8)	−0.0014 (8)	−0.0038 (8)
N2	0.0165 (11)	0.0171 (10)	0.0187 (10)	−0.0014 (8)	−0.0011 (8)	−0.0024 (8)
O1	0.0279 (10)	0.0191 (9)	0.0212 (9)	−0.0042 (8)	−0.0045 (8)	−0.0050 (7)
O2	0.0217 (9)	0.0193 (9)	0.0163 (9)	−0.0035 (7)	−0.0004 (7)	−0.0026 (7)
Br1	0.02871 (16)	0.02031 (14)	0.02034 (14)	0.00082 (10)	0.00016 (10)	0.00063 (10)

Geometric parameters (Å, º)

C1—C2	1.389 (4)	C8—O1	1.228 (3)
C1—C6	1.394 (4)	C8—N1	1.368 (3)
C1—Br1	1.911 (3)	C8—C9	1.502 (3)
C2—C3	1.382 (4)	C9—C10	1.375 (3)
C2—H2	0.9500	C9—C13	1.439 (3)
C3—C4	1.382 (4)	C10—C11	1.401 (4)
C3—H3	0.9500	C10—H10	0.9500
C4—C5	1.398 (3)	C11—C12	1.359 (4)
C4—H4	0.9500	C11—H11	0.9500
C5—N1	1.403 (3)	C12—N2	1.353 (3)
C5—C6	1.414 (3)	C12—H12	0.9500
C6—C7	1.509 (3)	C13—O2	1.259 (3)
C7—H7A	0.9800	C13—N2	1.371 (3)
C7—H7B	0.9800	N1—H1	0.8800
C7—H7C	0.9800	N2—H2A	0.8800
C2—C1—C6	123.6 (2)	O1—C8—N1	124.9 (2)
C2—C1—Br1	115.94 (19)	O1—C8—C9	121.1 (2)
C6—C1—Br1	120.48 (19)	N1—C8—C9	114.0 (2)
C3—C2—C1	118.1 (2)	C10—C9—C13	118.9 (2)
C3—C2—H2	121.0	C10—C9—C8	117.7 (2)
C1—C2—H2	121.0	C13—C9—C8	123.4 (2)
C4—C3—C2	121.1 (2)	C9—C10—C11	122.3 (2)
C4—C3—H3	119.4	C9—C10—H10	118.8
C2—C3—H3	119.4	C11—C10—H10	118.8
C3—C4—C5	119.9 (2)	C12—C11—C10	117.9 (2)
C3—C4—H4	120.0	C12—C11—H11	121.1
C5—C4—H4	120.0	C10—C11—H11	121.1
C4—C5—N1	122.4 (2)	N2—C12—C11	120.5 (2)
C4—C5—C6	120.8 (2)	N2—C12—H12	119.8
N1—C5—C6	116.7 (2)	C11—C12—H12	119.8
C1—C6—C5	116.5 (2)	O2—C13—N2	118.3 (2)
C1—C6—C7	123.5 (2)	O2—C13—C9	125.9 (2)
C5—C6—C7	120.1 (2)	N2—C13—C9	115.8 (2)
C6—C7—H7A	109.5	C8—N1—C5	129.5 (2)
C6—C7—H7B	109.5	C8—N1—H1	115.2
H7A—C7—H7B	109.5	C5—N1—H1	115.2
C6—C7—H7C	109.5	C12—N2—C13	124.7 (2)
H7A—C7—H7C	109.5	C12—N2—H2A	117.7
H7B—C7—H7C	109.5	C13—N2—H2A	117.7
C6—C1—C2—C3	−0.5 (4)	N1—C8—C9—C13	5.0 (3)
Br1—C1—C2—C3	179.22 (18)	C13—C9—C10—C11	−0.1 (4)
C1—C2—C3—C4	0.5 (4)	C8—C9—C10—C11	179.8 (2)
C2—C3—C4—C5	−0.5 (4)	C9—C10—C11—C12	0.1 (4)
C3—C4—C5—N1	179.1 (2)	C10—C11—C12—N2	−0.1 (4)
C3—C4—C5—C6	0.4 (4)	C10—C9—C13—O2	−179.7 (2)
C2—C1—C6—C5	0.4 (4)	C8—C9—C13—O2	0.4 (4)
Br1—C1—C6—C5	−179.30 (17)	C10—C9—C13—N2	0.2 (3)
C2—C1—C6—C7	−179.9 (2)	C8—C9—C13—N2	−179.7 (2)
Br1—C1—C6—C7	0.4 (3)	O1—C8—N1—C5	0.3 (4)
C4—C5—C6—C1	−0.4 (3)	C9—C8—N1—C5	179.9 (2)
N1—C5—C6—C1	−179.1 (2)	C4—C5—N1—C8	4.3 (4)
C4—C5—C6—C7	179.9 (2)	C6—C5—N1—C8	−177.0 (2)
N1—C5—C6—C7	1.1 (3)	C11—C12—N2—C13	0.2 (4)
O1—C8—C9—C10	4.8 (4)	O2—C13—N2—C12	179.7 (2)
N1—C8—C9—C10	−174.9 (2)	C9—C13—N2—C12	−0.2 (3)
O1—C8—C9—C13	−175.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2	0.88	1.90	2.660 (3)	144
N2—H2A···O2i	0.88	1.91	2.785 (3)	171

Symmetry code: (i) −x+1, −y+2, −z+1.