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

Dahmani, S.; Haoudi, A.; Capet, F.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810007695

organic compounds

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Volume 66| Part 4| April 2010| Page o755

doi:10.1107/S1600536810007695

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

S. Dahmani,^a A. Haoudi,^a F. 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, 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 22 February 2010; accepted 1 March 2010; online 6 March 2010)

The reaction of propargyl bromide and 6-bromo-1,3-dihydroimidazo[4,5-b]pyridin-2-one in refluxing dimethylformamide yields the title compound, C₁₂H₈BrN₃O, which features nitrogen-bound propadienyl and propynyl substituents. The imidazolopyridine fused ring is planar (r.m.s. deviation = 0.012 Å); the propadienyl chain is coplanar with the fused ring as it is conjugated with it, whereas the propynyl chain is not as the nitrogen-bound C atom is a methylene linkage. The acetylenic H atom is hydrogen bonded to the carbonyl O atom of an adjacent molecule, forming a helical chain runnning along the b axis.

Related literature

For the crystal structures of other imidazo[4,5-b]pyridin-2-ones, see: Kourafalos et al. (2002 ); Meanwell et al. (1995 ).

Experimental

Crystal data

C₁₂H₈BrN₃O
M_r = 290.12
Monoclinic, P 2₁ /n
a = 9.6369 (4) Å
b = 9.3086 (4) Å
c = 13.5481 (5) Å
β = 99.123 (2)°
V = 1199.97 (8) Å³
Z = 4
Mo Kα radiation
μ = 3.41 mm⁻¹
T = 293 K
0.55 × 0.35 × 0.30 mm

Data collection

Bruker X8 APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.256, T_max = 0.428
51411 measured reflections
3393 independent reflections
2577 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.087
S = 1.02
3393 reflections
166 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.49 e Å⁻³
Δρ_min = −0.63 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C12—H12⋯O1ⁱ	0.94 (1)	2.22 (1)	3.161 (3)	173 (2)
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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: 10.1107/S1600536810007695/hg2649sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810007695/hg2649Isup2.hkl

checkCIF report

Related literature top

For the crystal structures of other imidazo[4,5-b]pyridin-2-ones, see: Kourafalos et al. (2002); Meanwell et al. (1995).

Experimental top

To a solution of 6-bromo-1,3-dihydro-imidazo[4,5-b]pyridin-2-one (1 mmol), potassium carbonate (4 mmol) and tetra-n-butylammonium bromide (0.1 mmol) in DMF (20 ml) was added propargyl bromide (2.5 mmol). The solution was refluxed for 48 hours. After completion of the reaction (as monitored byTLC), the salt was filtered and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel by using an ethyl acetate/hexane (1/1) mixture as eluent. Slow evaporation of the solvent furnished colorless crystals.

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. Thermal ellipsoid plot (Barbour, 2001) of C₁₂H₈BrN₃O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

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

Crystal data top

C₁₂H₈BrN₃O	F(000) = 576
M_r = 290.12	D_x = 1.606 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9975 reflections
a = 9.6369 (4) Å	θ = 2.4–25.6°
b = 9.3086 (4) Å	µ = 3.41 mm⁻¹
c = 13.5481 (5) Å	T = 293 K
β = 99.123 (2)°	Irregular, colorless
V = 1199.97 (8) Å³	0.55 × 0.35 × 0.30 mm
Z = 4

Data collection top

Bruker X8 APEXII diffractometer	3393 independent reflections
Radiation source: fine-focus sealed tube	2577 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ϕ and ω scans	θ_max = 29.7°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −13→13
T_min = 0.256, T_max = 0.428	k = −12→12
51411 measured reflections	l = −18→18

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)] = 0.031	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0413P)² + 0.4635P] where P = (F_o² + 2F_c²)/3
3393 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.49 e Å⁻³
3 restraints	Δρ_min = −0.63 e Å⁻³

Crystal data top

C₁₂H₈BrN₃O	V = 1199.97 (8) Å³
M_r = 290.12	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6369 (4) Å	µ = 3.41 mm⁻¹
b = 9.3086 (4) Å	T = 293 K
c = 13.5481 (5) Å	0.55 × 0.35 × 0.30 mm
β = 99.123 (2)°

Data collection top

Bruker X8 APEXII diffractometer	3393 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2577 reflections with I > 2σ(I)
T_min = 0.256, T_max = 0.428	R_int = 0.040
51411 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	3 restraints
wR(F²) = 0.087	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.49 e Å⁻³
3393 reflections	Δρ_min = −0.63 e Å⁻³
166 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.40648 (3)	0.39876 (3)	0.231050 (17)	0.06785 (11)
O1	0.49655 (17)	0.95432 (17)	0.64205 (11)	0.0577 (4)
N1	0.21863 (16)	0.64109 (19)	0.42594 (13)	0.0453 (4)
N2	0.54742 (15)	0.78896 (16)	0.52363 (11)	0.0395 (3)
N3	0.32605 (16)	0.81244 (17)	0.54674 (11)	0.0417 (3)
C1	0.2477 (2)	0.5495 (2)	0.35479 (15)	0.0490 (4)
H1	0.1744	0.4972	0.3188	0.059*
C2	0.3815 (2)	0.53039 (19)	0.33326 (13)	0.0435 (4)
C3	0.4981 (2)	0.60309 (19)	0.38454 (13)	0.0399 (4)
H3	0.5887	0.5895	0.3708	0.048*
C4	0.46792 (17)	0.69616 (18)	0.45684 (12)	0.0346 (3)
C5	0.32815 (18)	0.71031 (18)	0.47294 (12)	0.0365 (3)
C6	0.6938 (2)	0.8150 (2)	0.53701 (16)	0.0503 (5)
H6	0.7302	0.8828	0.5845	0.060*
C7	0.7806 (2)	0.7510 (2)	0.48776 (17)	0.0529 (5)
C8	0.8709 (3)	0.6872 (4)	0.4413 (2)	0.0750 (8)
H81	0.916 (3)	0.602 (2)	0.467 (3)	0.106 (12)*
H82	0.890 (3)	0.722 (3)	0.3788 (13)	0.089 (10)*
C9	0.4605 (2)	0.8628 (2)	0.57909 (14)	0.0416 (4)
C10	0.2020 (2)	0.8584 (2)	0.58740 (16)	0.0509 (5)
H10A	0.1252	0.8736	0.5328	0.061*
H10B	0.2218	0.9494	0.6217	0.061*
C11	0.1586 (2)	0.7538 (2)	0.65707 (15)	0.0521 (5)
C12	0.1208 (3)	0.6715 (3)	0.71186 (19)	0.0694 (7)
H12	0.093 (3)	0.601 (2)	0.7550 (18)	0.088 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0918 (2)	0.05653 (15)	0.05116 (14)	0.01376 (12)	−0.00107 (12)	−0.01710 (9)
O1	0.0645 (9)	0.0499 (8)	0.0563 (9)	0.0031 (7)	0.0024 (7)	−0.0158 (7)
N1	0.0357 (8)	0.0481 (9)	0.0513 (9)	−0.0027 (7)	0.0046 (7)	0.0022 (7)
N2	0.0367 (7)	0.0396 (8)	0.0417 (7)	−0.0023 (6)	0.0050 (6)	−0.0021 (6)
N3	0.0417 (8)	0.0425 (8)	0.0431 (8)	0.0011 (6)	0.0133 (6)	−0.0014 (6)
C1	0.0469 (10)	0.0461 (10)	0.0504 (10)	−0.0050 (8)	−0.0035 (8)	−0.0017 (8)
C2	0.0555 (11)	0.0369 (9)	0.0362 (8)	0.0034 (8)	0.0016 (7)	−0.0014 (7)
C3	0.0408 (9)	0.0411 (9)	0.0385 (8)	0.0031 (7)	0.0085 (7)	0.0024 (7)
C4	0.0351 (8)	0.0350 (8)	0.0334 (7)	−0.0008 (6)	0.0051 (6)	0.0060 (6)
C5	0.0386 (8)	0.0350 (8)	0.0364 (8)	0.0006 (7)	0.0079 (6)	0.0057 (6)
C6	0.0381 (9)	0.0515 (11)	0.0592 (12)	−0.0078 (8)	0.0015 (8)	−0.0032 (9)
C7	0.0343 (9)	0.0597 (12)	0.0628 (12)	−0.0064 (9)	0.0017 (9)	0.0098 (10)
C8	0.0396 (11)	0.101 (2)	0.0867 (19)	0.0039 (13)	0.0176 (12)	0.0060 (17)
C9	0.0474 (10)	0.0370 (9)	0.0402 (9)	0.0029 (7)	0.0061 (7)	0.0014 (7)
C10	0.0512 (11)	0.0491 (11)	0.0570 (12)	0.0097 (9)	0.0224 (9)	0.0029 (9)
C11	0.0510 (11)	0.0614 (12)	0.0461 (10)	0.0007 (9)	0.0149 (8)	−0.0033 (9)
C12	0.0748 (16)	0.0808 (18)	0.0555 (13)	−0.0120 (14)	0.0197 (12)	0.0087 (12)

Geometric parameters (Å, º) top

Br1—C2	1.8928 (18)	C3—C4	1.373 (2)
O1—C9	1.216 (2)	C3—H3	0.9300
N1—C5	1.312 (2)	C4—C5	1.404 (2)
N1—C1	1.349 (3)	C6—C7	1.295 (3)
N2—C4	1.390 (2)	C6—H6	0.9300
N2—C9	1.393 (2)	C7—C8	1.296 (4)
N2—C6	1.414 (2)	C8—H81	0.95 (1)
N3—C5	1.382 (2)	C8—H82	0.95 (1)
N3—C9	1.382 (2)	C10—C11	1.463 (3)
N3—C10	1.458 (2)	C10—H10A	0.9700
C1—C2	1.378 (3)	C10—H10B	0.9700
C1—H1	0.9300	C11—C12	1.164 (3)
C2—C3	1.398 (3)	C12—H12	0.94 (1)

C5—N1—C1	114.50 (16)	N1—C5—C4	126.59 (17)
C4—N2—C9	109.96 (14)	N3—C5—C4	107.53 (15)
C4—N2—C6	128.72 (16)	C7—C6—N2	124.62 (19)
C9—N2—C6	121.29 (16)	C7—C6—H6	117.7
C5—N3—C9	110.03 (15)	N2—C6—H6	117.7
C5—N3—C10	125.63 (16)	C8—C7—C6	178.0 (3)
C9—N3—C10	124.33 (16)	C7—C8—H81	121 (2)
N1—C1—C2	122.72 (18)	C7—C8—H82	120.7 (19)
N1—C1—H1	118.6	H81—C8—H82	118 (3)
C2—C1—H1	118.6	O1—C9—N3	127.55 (18)
C1—C2—C3	122.49 (17)	O1—C9—N2	126.48 (18)
C1—C2—Br1	118.07 (14)	N3—C9—N2	105.97 (15)
C3—C2—Br1	119.43 (14)	N3—C10—C11	112.56 (17)
C4—C3—C2	114.56 (16)	N3—C10—H10A	109.1
C4—C3—H3	122.7	C11—C10—H10A	109.1
C2—C3—H3	122.7	N3—C10—H10B	109.1
C3—C4—N2	134.39 (16)	C11—C10—H10B	109.1
C3—C4—C5	119.12 (16)	H10A—C10—H10B	107.8
N2—C4—C5	106.49 (15)	C12—C11—C10	178.4 (3)
N1—C5—N3	125.87 (16)	C11—C12—H12	177.2 (19)

C5—N1—C1—C2	0.0 (3)	C3—C4—C5—N1	0.9 (3)
N1—C1—C2—C3	0.9 (3)	N2—C4—C5—N1	−179.58 (17)
N1—C1—C2—Br1	−179.76 (15)	C3—C4—C5—N3	−178.29 (15)
C1—C2—C3—C4	−0.8 (3)	N2—C4—C5—N3	1.26 (18)
Br1—C2—C3—C4	179.81 (12)	C4—N2—C6—C7	−1.4 (3)
C2—C3—C4—N2	−179.36 (18)	C9—N2—C6—C7	−179.6 (2)
C2—C3—C4—C5	0.0 (2)	C5—N3—C9—O1	178.90 (19)
C9—N2—C4—C3	178.04 (18)	C10—N3—C9—O1	−2.7 (3)
C6—N2—C4—C3	−0.3 (3)	C5—N3—C9—N2	−0.2 (2)
C9—N2—C4—C5	−1.41 (19)	C10—N3—C9—N2	178.17 (16)
C6—N2—C4—C5	−179.75 (17)	C4—N2—C9—O1	−178.10 (19)
C1—N1—C5—N3	178.16 (17)	C6—N2—C9—O1	0.4 (3)
C1—N1—C5—C4	−0.9 (3)	C4—N2—C9—N3	1.00 (19)
C9—N3—C5—N1	−179.84 (17)	C6—N2—C9—N3	179.49 (16)
C10—N3—C5—N1	1.8 (3)	C5—N3—C10—C11	76.4 (2)
C9—N3—C5—C4	−0.67 (19)	C9—N3—C10—C11	−101.7 (2)
C10—N3—C5—C4	−179.00 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C12—H12···O1ⁱ	0.94 (1)	2.22 (1)	3.161 (3)	173 (2)

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₈BrN₃O
M_r	290.12
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	9.6369 (4), 9.3086 (4), 13.5481 (5)
β (°)	99.123 (2)
V (Å³)	1199.97 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	3.41
Crystal size (mm)	0.55 × 0.35 × 0.30

Data collection
Diffractometer	Bruker X8 APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.256, 0.428
No. of measured, independent and observed [I > 2σ(I)] reflections	51411, 3393, 2577
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.697

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.087, 1.02
No. of reflections	3393
No. of parameters	166
No. of restraints	3
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.49, −0.63

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
C12—H12···O1ⁱ	0.94 (1)	2.22 (1)	3.161 (3)	173 (2)

Symmetry code: (i) −x+1/2, y−1/2, −z+3/2.

Acknowledgements

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

References

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