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Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o755.
Published online 2010 March 6. doi:  10.1107/S1600536810007695
PMCID: PMC2983773

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

Abstract

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 [triangle]); Meanwell et al. (1995 [triangle]).

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Object name is e-66-0o755-scheme1.jpg

Experimental

Crystal data

  • C12H8BrN3O
  • M r = 290.12
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o755-efi1.jpg
  • 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 [triangle]) 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 [triangle]); cell refinement: SAINT (Bruker, 2008 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: X-SEED (Barbour, 2001 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

Acknowledgments

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

supplementary crystallographic information

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The terminal acetylenic and allenic H-atoms were located in a difference Fourier map, and were refined with a distance restraint of C–H 0.95±0.01 Å; their temperature factors were refined.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C12H8BrN3O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C12H8BrN3OF(000) = 576
Mr = 290.12Dx = 1.606 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 9975 reflections
a = 9.6369 (4) Åθ = 2.4–25.6°
b = 9.3086 (4) ŵ = 3.41 mm1
c = 13.5481 (5) ÅT = 293 K
β = 99.123 (2)°Irregular, colorless
V = 1199.97 (8) Å30.55 × 0.35 × 0.30 mm
Z = 4

Data collection

Bruker X8 APEXII diffractometer3393 independent reflections
Radiation source: fine-focus sealed tube2577 reflections with I > 2σ(I)
graphiteRint = 0.040
[var phi] and ω scansθmax = 29.7°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −13→13
Tmin = 0.256, Tmax = 0.428k = −12→12
51411 measured reflectionsl = −18→18

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.087H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0413P)2 + 0.4635P] where P = (Fo2 + 2Fc2)/3
3393 reflections(Δ/σ)max = 0.001
166 parametersΔρmax = 0.49 e Å3
3 restraintsΔρmin = −0.63 e Å3

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

xyzUiso*/Ueq
Br10.40648 (3)0.39876 (3)0.231050 (17)0.06785 (11)
O10.49655 (17)0.95432 (17)0.64205 (11)0.0577 (4)
N10.21863 (16)0.64109 (19)0.42594 (13)0.0453 (4)
N20.54742 (15)0.78896 (16)0.52363 (11)0.0395 (3)
N30.32605 (16)0.81244 (17)0.54674 (11)0.0417 (3)
C10.2477 (2)0.5495 (2)0.35479 (15)0.0490 (4)
H10.17440.49720.31880.059*
C20.3815 (2)0.53039 (19)0.33326 (13)0.0435 (4)
C30.4981 (2)0.60309 (19)0.38454 (13)0.0399 (4)
H30.58870.58950.37080.048*
C40.46792 (17)0.69616 (18)0.45684 (12)0.0346 (3)
C50.32815 (18)0.71031 (18)0.47294 (12)0.0365 (3)
C60.6938 (2)0.8150 (2)0.53701 (16)0.0503 (5)
H60.73020.88280.58450.060*
C70.7806 (2)0.7510 (2)0.48776 (17)0.0529 (5)
C80.8709 (3)0.6872 (4)0.4413 (2)0.0750 (8)
H810.916 (3)0.602 (2)0.467 (3)0.106 (12)*
H820.890 (3)0.722 (3)0.3788 (13)0.089 (10)*
C90.4605 (2)0.8628 (2)0.57909 (14)0.0416 (4)
C100.2020 (2)0.8584 (2)0.58740 (16)0.0509 (5)
H10A0.12520.87360.53280.061*
H10B0.22180.94940.62170.061*
C110.1586 (2)0.7538 (2)0.65707 (15)0.0521 (5)
C120.1208 (3)0.6715 (3)0.71186 (19)0.0694 (7)
H120.093 (3)0.601 (2)0.7550 (18)0.088 (11)*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0918 (2)0.05653 (15)0.05116 (14)0.01376 (12)−0.00107 (12)−0.01710 (9)
O10.0645 (9)0.0499 (8)0.0563 (9)0.0031 (7)0.0024 (7)−0.0158 (7)
N10.0357 (8)0.0481 (9)0.0513 (9)−0.0027 (7)0.0046 (7)0.0022 (7)
N20.0367 (7)0.0396 (8)0.0417 (7)−0.0023 (6)0.0050 (6)−0.0021 (6)
N30.0417 (8)0.0425 (8)0.0431 (8)0.0011 (6)0.0133 (6)−0.0014 (6)
C10.0469 (10)0.0461 (10)0.0504 (10)−0.0050 (8)−0.0035 (8)−0.0017 (8)
C20.0555 (11)0.0369 (9)0.0362 (8)0.0034 (8)0.0016 (7)−0.0014 (7)
C30.0408 (9)0.0411 (9)0.0385 (8)0.0031 (7)0.0085 (7)0.0024 (7)
C40.0351 (8)0.0350 (8)0.0334 (7)−0.0008 (6)0.0051 (6)0.0060 (6)
C50.0386 (8)0.0350 (8)0.0364 (8)0.0006 (7)0.0079 (6)0.0057 (6)
C60.0381 (9)0.0515 (11)0.0592 (12)−0.0078 (8)0.0015 (8)−0.0032 (9)
C70.0343 (9)0.0597 (12)0.0628 (12)−0.0064 (9)0.0017 (9)0.0098 (10)
C80.0396 (11)0.101 (2)0.0867 (19)0.0039 (13)0.0176 (12)0.0060 (17)
C90.0474 (10)0.0370 (9)0.0402 (9)0.0029 (7)0.0061 (7)0.0014 (7)
C100.0512 (11)0.0491 (11)0.0570 (12)0.0097 (9)0.0224 (9)0.0029 (9)
C110.0510 (11)0.0614 (12)0.0461 (10)0.0007 (9)0.0149 (8)−0.0033 (9)
C120.0748 (16)0.0808 (18)0.0555 (13)−0.0120 (14)0.0197 (12)0.0087 (12)

Geometric parameters (Å, °)

Br1—C21.8928 (18)C3—C41.373 (2)
O1—C91.216 (2)C3—H30.9300
N1—C51.312 (2)C4—C51.404 (2)
N1—C11.349 (3)C6—C71.295 (3)
N2—C41.390 (2)C6—H60.9300
N2—C91.393 (2)C7—C81.296 (4)
N2—C61.414 (2)C8—H810.95 (1)
N3—C51.382 (2)C8—H820.95 (1)
N3—C91.382 (2)C10—C111.463 (3)
N3—C101.458 (2)C10—H10A0.9700
C1—C21.378 (3)C10—H10B0.9700
C1—H10.9300C11—C121.164 (3)
C2—C31.398 (3)C12—H120.94 (1)
C5—N1—C1114.50 (16)N1—C5—C4126.59 (17)
C4—N2—C9109.96 (14)N3—C5—C4107.53 (15)
C4—N2—C6128.72 (16)C7—C6—N2124.62 (19)
C9—N2—C6121.29 (16)C7—C6—H6117.7
C5—N3—C9110.03 (15)N2—C6—H6117.7
C5—N3—C10125.63 (16)C8—C7—C6178.0 (3)
C9—N3—C10124.33 (16)C7—C8—H81121 (2)
N1—C1—C2122.72 (18)C7—C8—H82120.7 (19)
N1—C1—H1118.6H81—C8—H82118 (3)
C2—C1—H1118.6O1—C9—N3127.55 (18)
C1—C2—C3122.49 (17)O1—C9—N2126.48 (18)
C1—C2—Br1118.07 (14)N3—C9—N2105.97 (15)
C3—C2—Br1119.43 (14)N3—C10—C11112.56 (17)
C4—C3—C2114.56 (16)N3—C10—H10A109.1
C4—C3—H3122.7C11—C10—H10A109.1
C2—C3—H3122.7N3—C10—H10B109.1
C3—C4—N2134.39 (16)C11—C10—H10B109.1
C3—C4—C5119.12 (16)H10A—C10—H10B107.8
N2—C4—C5106.49 (15)C12—C11—C10178.4 (3)
N1—C5—N3125.87 (16)C11—C12—H12177.2 (19)
C5—N1—C1—C20.0 (3)C3—C4—C5—N10.9 (3)
N1—C1—C2—C30.9 (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—N31.26 (18)
Br1—C2—C3—C4179.81 (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—C50.0 (2)C5—N3—C9—O1178.90 (19)
C9—N2—C4—C3178.04 (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—N2178.17 (16)
C6—N2—C4—C5−179.75 (17)C4—N2—C9—O1−178.10 (19)
C1—N1—C5—N3178.16 (17)C6—N2—C9—O10.4 (3)
C1—N1—C5—C4−0.9 (3)C4—N2—C9—N31.00 (19)
C9—N3—C5—N1−179.84 (17)C6—N2—C9—N3179.49 (16)
C10—N3—C5—N11.8 (3)C5—N3—C10—C1176.4 (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, °)

D—H···AD—HH···AD···AD—H···A
C12—H12···O1i0.94 (1)2.22 (1)3.161 (3)173 (2)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HG2649).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Kourafalos, V. N., Marakos, P., Pouli, N., Terzis, A. & Townsend, L. B. (2002). Heterocycles, 57, 2335–2343.
  • Meanwell, N. A., Sit, S. Y., Gao, J. N., Wong, H. S., Gao, Q., St Laurent, D. R. & Balasubramanian, N. (1995). J. Org. Chem.50, 1565–1582.
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). publCIF In preparation.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography