6-Bromo-1-(1,2-propadien-yl)-3-(2-propyn-yl)-1H-imidazo[4,5-b]pyridin-2(3H)-one.

The reaction of propargyl bromide and 6-bromo-1,3-dihydro-imidazo[4,5-b]pyridin-2-one in refluxing dimethyl-formamide yields the title compound, C(12)H(8)BrN(3)O, which features nitro-gen-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 nitro-gen-bound C atom is a methyl-ene linkage. The acetyl-enic H atom is hydrogen bonded to the carbonyl O atom of an adjacent mol-ecule, 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 = 290.12

Monoclinic,

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[F 2 > 2σ(F 2)] = 0.031

wR(F 2) = 0.087

S = 1.02

3393 reflections

166 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.63 e Å−3

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 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810007695/hg2649sup1.cif

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

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

C12H8BrN3O	F(000) = 576
Mr = 290.12	Dx = 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

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

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(Fo2) + (0.0413P)2 + 0.4635P] where P = (Fo2 + 2Fc2)/3
3393 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.49 e Å−3
3 restraints	Δρmin = −0.63 e Å−3

	x	y	z	Uiso*/Ueq
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)*

	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)

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)

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)

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) .