6-Bromo-3-methyl-1H-imidazo[4,5-b]pyridin-2(3H)-one

Ghacham, H.B.; Rodi, Y.K.; Capet, F.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810012791

organic compounds

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ISSN: 2056-9890

Volume 66| Part 5| May 2010| Page o1080

https://doi.org/10.1107/S1600536810012791

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6-Bromo-3-methyl-1H-imidazo[4,5-b]pyridin-2(3H)-one

Hend Bel Ghacham,^a Youssef Kandri Rodi,^a Frédéric Capet,^b El Mokhtar Essassi ^c and Seik Weng Ng ^d ^*

^aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fés, Morocco, ^bUnité de Catalyse et de Chimie du Solide (UCCS), UMR 8181, Ecole Nationale Supérieure de Chimie de Lille, Lille, France, ^cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 6 April 2010; accepted 6 April 2010; online 14 April 2010)

The title compound, C₇H₆BrN₃O, was obtained from the reaction of 6-bromo-1H-imidazo[4,5-b]pyridin-2(3H)-one with methyl iodide. All non-H atoms lie in a common plane [r.m.s deviation = 0.017 (1) Å]. The amino group is a hydrogen-bond donor to the carbonyl group of an inversion-related molecule, the pair of hydrogen bonds giving rise to a hydrogen-bonded dimer.

Related literature

For the synthesis of the title compound, see: Grivas & Lindström (1995 ); Smolyar et al. (2007 ).

Experimental

Crystal data

C₇H₆BrN₃O
M_r = 228.06
Triclinic, $[P \overline 1]$
a = 4.4151 (1) Å
b = 9.6004 (2) Å
c = 10.5330 (3) Å
α = 116.248 (1)°
β = 93.074 (2)°
γ = 91.687 (1)°
V = 399.14 (2) Å³
Z = 2
Mo Kα radiation
μ = 5.10 mm⁻¹
T = 293 K
0.36 × 0.17 × 0.10 mm

Data collection

Bruker X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.478, T_max = 0.630
4790 measured reflections
1401 independent reflections
1199 reflections with I > 2σ(I)
R_int = 0.027
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.077
S = 1.05
1401 reflections
114 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O1ⁱ	0.86 (1)	1.95 (1)	2.804 (3)	176 (4)
Symmetry code: (i) -x, -y+1, -z+1.

Data collection: APEX2 (Bruker, 2008 ); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001 ); software used to prepare material for publication: publCIF (Westrip, 2010 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810012791/bt5243sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810012791/bt5243Isup2.hkl

checkCIF report

Comment top

6-Bromo-1H-imidazo[4,5-b]pyridine-2(3H)-one reacts with organic compounds to form pharmaceutical active compounds. It is easily methylated; in this study, it is methylated by methyl iodide under catalytic conditions. The mono N-methylated compound (Scheme I) is planar [r.m.s 0.017 (1) Å]. The amino group is hydrogen-bond donor to the carbonyl group of an inversion-related molecule to generate a hydrogen-bonded dimer (Fig. 1).

Related literature top

For the synthesis of the title compound, see: Grivas & Lindström (1995); Smolyar et al. (2007).

Experimental top

6-Bromo-1H-imidazo[4,5-b]pyridine-2(3H)-thione (1 mmol), potassium carbonate (4 mmol), tetra-n-butylammonium bromide (0.1 mmol) and methyl iodide (2.5 mmol) in DMF (15 ml) were stirred for 48 hours. After completion of reaction (as monitored by TLC), the salt was filtered and the solvent removed under reduced pressure. The resulting residue was purified by column chromatography on silica gel using ethyl acetate/hexane (1/2) as eluent. Yellow crystals was isolated when the solvent was allowed to evaporate.

Structure description top

For the synthesis of the title compound, see: Grivas & Lindström (1995); Smolyar et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2010).

Figures top

Fig. 1. Anisotropic displacement ellipsoid plot (Barbour, 2001) of the title compound forming a centrosymmetric dimer at the 50% probability level; H atoms are drawn as spheres of arbitrary radii.

6-Bromo-3-methyl-1H-imidazo[4,5-b]pyridin-2(3H)-one top

Crystal data top

C₇H₆BrN₃O	Z = 2
M_r = 228.06	F(000) = 224
Triclinic, P1	D_x = 1.898 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 4.4151 (1) Å	Cell parameters from 2054 reflections
b = 9.6004 (2) Å	θ = 2.4–24.1°
c = 10.5330 (3) Å	µ = 5.10 mm⁻¹
α = 116.248 (1)°	T = 293 K
β = 93.074 (2)°	Prism, yellow
γ = 91.687 (1)°	0.36 × 0.17 × 0.10 mm
V = 399.14 (2) Å³

Data collection top

Bruker X8 APEXII diffractometer	1401 independent reflections
Radiation source: fine-focus sealed tube	1199 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 24.9°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→4
T_min = 0.478, T_max = 0.630	k = −11→11
4790 measured reflections	l = −12→12

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0493P)² + 0.0118P] where P = (F_o² + 2F_c²)/3
1401 reflections	(Δ/σ)_max = 0.001
114 parameters	Δρ_max = 0.52 e Å⁻³
1 restraint	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₇H₆BrN₃O	γ = 91.687 (1)°
M_r = 228.06	V = 399.14 (2) Å³
Triclinic, P1	Z = 2
a = 4.4151 (1) Å	Mo Kα radiation
b = 9.6004 (2) Å	µ = 5.10 mm⁻¹
c = 10.5330 (3) Å	T = 293 K
α = 116.248 (1)°	0.36 × 0.17 × 0.10 mm
β = 93.074 (2)°

Data collection top

Bruker X8 APEXII diffractometer	1401 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1199 reflections with I > 2σ(I)
T_min = 0.478, T_max = 0.630	R_int = 0.027
4790 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	1 restraint
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.52 e Å⁻³
1401 reflections	Δρ_min = −0.32 e Å⁻³
114 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.91934 (8)	0.96903 (4)	0.29671 (4)	0.04832 (17)
O1	0.0726 (5)	0.3085 (3)	0.3562 (3)	0.0478 (6)
N1	0.7410 (6)	0.4941 (3)	0.1298 (3)	0.0393 (6)
N2	0.4091 (6)	0.3574 (3)	0.2169 (3)	0.0368 (6)
N3	0.2638 (6)	0.5575 (3)	0.4045 (3)	0.0373 (6)
H3	0.165 (7)	0.603 (4)	0.478 (2)	0.052 (11)*
C1	0.8436 (8)	0.6389 (4)	0.1562 (3)	0.0395 (8)
H1	0.9737	0.6506	0.0946	0.047*
C2	0.7621 (7)	0.7715 (4)	0.2724 (3)	0.0362 (7)
C3	0.5682 (7)	0.7635 (3)	0.3680 (3)	0.0357 (7)
H3A	0.5157	0.8517	0.4462	0.043*
C4	0.4584 (7)	0.6171 (4)	0.3399 (3)	0.0332 (7)
C5	0.5521 (7)	0.4890 (4)	0.2200 (3)	0.0326 (7)
C6	0.2306 (7)	0.3988 (4)	0.3293 (3)	0.0359 (7)
C7	0.4409 (9)	0.1982 (4)	0.1123 (4)	0.0532 (10)
H7A	0.6141	0.1577	0.1406	0.080*
H7B	0.4681	0.1960	0.0216	0.080*
H7C	0.2613	0.1357	0.1055	0.080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0551 (3)	0.0388 (2)	0.0537 (3)	−0.00649 (16)	0.00846 (17)	0.02302 (18)
O1	0.0560 (15)	0.0356 (12)	0.0502 (14)	−0.0057 (11)	0.0173 (12)	0.0168 (11)
N1	0.0399 (15)	0.0385 (15)	0.0382 (15)	0.0040 (12)	0.0119 (12)	0.0146 (13)
N2	0.0420 (15)	0.0298 (13)	0.0356 (14)	0.0018 (11)	0.0087 (12)	0.0112 (11)
N3	0.0406 (16)	0.0336 (14)	0.0361 (15)	0.0011 (12)	0.0140 (13)	0.0131 (12)
C1	0.0404 (18)	0.0410 (18)	0.0380 (18)	0.0024 (14)	0.0119 (15)	0.0175 (16)
C2	0.0372 (17)	0.0328 (16)	0.0416 (19)	−0.0016 (13)	0.0022 (15)	0.0194 (15)
C3	0.0367 (17)	0.0305 (16)	0.0381 (17)	0.0040 (13)	0.0074 (14)	0.0131 (14)
C4	0.0294 (16)	0.0336 (16)	0.0353 (17)	0.0032 (13)	0.0029 (13)	0.0139 (14)
C5	0.0305 (16)	0.0308 (15)	0.0344 (16)	0.0030 (13)	0.0015 (13)	0.0126 (13)
C6	0.0349 (17)	0.0367 (17)	0.0357 (17)	0.0011 (14)	0.0064 (14)	0.0155 (14)
C7	0.067 (3)	0.0341 (18)	0.049 (2)	0.0033 (17)	0.0166 (19)	0.0079 (16)

Geometric parameters (Å, º) top

Br1—C2	1.902 (3)	C1—C2	1.394 (5)
O1—C6	1.233 (4)	C1—H1	0.9300
N1—C5	1.313 (4)	C2—C3	1.382 (4)
N1—C1	1.349 (4)	C3—C4	1.369 (4)
N2—C6	1.373 (4)	C3—H3A	0.9300
N2—C5	1.382 (4)	C4—C5	1.411 (4)
N2—C7	1.452 (4)	C7—H7A	0.9600
N3—C6	1.370 (4)	C7—H7B	0.9600
N3—C4	1.381 (4)	C7—H7C	0.9600
N3—H3	0.856 (10)

C5—N1—C1	114.5 (3)	C3—C4—N3	134.7 (3)
C6—N2—C5	109.8 (2)	C3—C4—C5	118.7 (3)
C6—N2—C7	124.2 (3)	N3—C4—C5	106.6 (3)
C5—N2—C7	126.1 (3)	N1—C5—N2	126.7 (3)
C6—N3—C4	110.0 (3)	N1—C5—C4	126.5 (3)
C6—N3—H3	119 (3)	N2—C5—C4	106.7 (3)
C4—N3—H3	131 (3)	O1—C6—N3	127.3 (3)
N1—C1—C2	122.5 (3)	O1—C6—N2	125.8 (3)
N1—C1—H1	118.7	N3—C6—N2	106.9 (3)
C2—C1—H1	118.7	N2—C7—H7A	109.5
C3—C2—C1	122.1 (3)	N2—C7—H7B	109.5
C3—C2—Br1	119.5 (2)	H7A—C7—H7B	109.5
C1—C2—Br1	118.4 (2)	N2—C7—H7C	109.5
C4—C3—C2	115.6 (3)	H7A—C7—H7C	109.5
C4—C3—H3A	122.2	H7B—C7—H7C	109.5
C2—C3—H3A	122.2

C5—N1—C1—C2	1.8 (5)	C6—N2—C5—C4	0.2 (3)
N1—C1—C2—C3	−0.5 (5)	C7—N2—C5—C4	−179.4 (3)
N1—C1—C2—Br1	−179.4 (2)	C3—C4—C5—N1	0.6 (5)
C1—C2—C3—C4	−0.9 (5)	N3—C4—C5—N1	−179.2 (3)
Br1—C2—C3—C4	178.0 (2)	C3—C4—C5—N2	−179.9 (3)
C2—C3—C4—N3	−179.4 (3)	N3—C4—C5—N2	0.3 (3)
C2—C3—C4—C5	0.8 (4)	C4—N3—C6—O1	−179.5 (3)
C6—N3—C4—C3	179.6 (3)	C4—N3—C6—N2	0.7 (4)
C6—N3—C4—C5	−0.6 (3)	C5—N2—C6—O1	179.7 (3)
C1—N1—C5—N2	178.8 (3)	C7—N2—C6—O1	−0.8 (5)
C1—N1—C5—C4	−1.9 (5)	C5—N2—C6—N3	−0.5 (3)
C6—N2—C5—N1	179.6 (3)	C7—N2—C6—N3	179.0 (3)
C7—N2—C5—N1	0.1 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.86 (1)	1.95 (1)	2.804 (3)	176 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₇H₆BrN₃O
M_r	228.06
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	4.4151 (1), 9.6004 (2), 10.5330 (3)
α, β, γ (°)	116.248 (1), 93.074 (2), 91.687 (1)
V (Å³)	399.14 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.10
Crystal size (mm)	0.36 × 0.17 × 0.10

Data collection
Diffractometer	Bruker X8 APEXII
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.478, 0.630
No. of measured, independent and observed [I > 2σ(I)] reflections	4790, 1401, 1199
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.593

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.077, 1.05
No. of reflections	1401
No. of parameters	114
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.32

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O1ⁱ	0.86 (1)	1.95 (1)	2.804 (3)	176 (4)

Symmetry code: (i) −x, −y+1, −z+1.

Acknowledgements

The authors thank the University Sidi Mohammed Ben Abdallah, the Université Mohammed V-Agdal and the University of Malaya for supporting this study.

References

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