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Acta Crystallogr Sect E Struct Rep Online. 2010 August 1; 66(Pt 8): o1904.
Published online 2010 July 3. doi:  10.1107/S1600536810025134
PMCID: PMC3007224

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

Abstract

The non-H atoms of the two independent mol­ecules in the asymmetric unit of the title compound, C8H8BrN3O, are planar (r.m.s. deviations = 0.015 and 0.019 Å). In the crystal, the mol­ecules are linked into a zigzag chain along the c axis by C—H(...)O hydrogen bonds.

Related literature

For the synthesis of the un-brominated compound, see: Yutilov et al. (1998 [triangle], 2005 [triangle]).

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Object name is e-66-o1904-scheme1.jpg

Experimental

Crystal data

  • C8H8BrN3O
  • M r = 242.08
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o1904-efi1.jpg
  • a = 21.7981 (4) Å
  • b = 3.9929 (1) Å
  • c = 20.6636 (3) Å
  • β = 95.398 (1)°
  • V = 1790.53 (6) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 4.55 mm−1
  • T = 293 K
  • 0.25 × 0.20 × 0.15 mm

Data collection

  • Bruker X8 APEXII area-detector diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.396, T max = 0.548
  • 21586 measured reflections
  • 5229 independent reflections
  • 3539 reflections with I > 2σ(I)
  • R int = 0.036

Refinement

  • R[F 2 > 2σ(F 2)] = 0.031
  • wR(F 2) = 0.086
  • S = 1.01
  • 5229 reflections
  • 239 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.29 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/S1600536810025134/ci5119sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810025134/ci5119Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

The imidazo[4,5-b]pyridine unit is an important heterocyclic nucleus found in a large number of medicinal compounds. The synthesis of 1,3-dimethyl-1,3-dihydro-imidazo[4,5-b]pyridin-2-one involves several steps (Yutilov et al., 1998, 2005). The 6-bromo derivative (Scheme I) is conveniently synthesized by the direct reaction of 6-bromo-1,3-dihydro-imidazo[4,5-b]pyridin-2-one with methyl iodide.

The aysmmetric unit (Fig. 1) has two independent molecules. Both are planar.

Experimental

To a mixture of 6-bromo-1,3-dihydro-imidazo[4,5-b]pyridin-2-one (0.15 g, 1 mmol), potassium carbonate (0.38 g, 4 mmol) and tetra-n-butylammonium bromide (0.02 g, 0.1 mmol) in DMF (10 ml) was added methyl iodide (0.1 ml, 2.5 mmol). Stirring was continued at room temperature for 12 h. After the completion of reaction (as monitored by TLC), the mixture was filtered and the solvent removed under reduced pressure. The residue was purified by column chromatography on silica gel with ethyl acetate-hexane (1:3) as eluent. The compound was recrystallized from ethyl acetate-hexane (1:3) to afford colourless crystals.

Refinement

H atoms were placed in calculated positions (C-H = 0.93–0.96 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2–1.5Ueq(C).

Figures

Fig. 1.
Displacement ellipsoid plot (Barbour, 2001) of the two independent molecules of C8H8BrN3O at the 50% probability level. H atoms are shown as spheres of arbitrary radii.

Crystal data

C8H8BrN3OF(000) = 960
Mr = 242.08Dx = 1.796 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6375 reflections
a = 21.7981 (4) Åθ = 2.6–25.2°
b = 3.9929 (1) ŵ = 4.55 mm1
c = 20.6636 (3) ÅT = 293 K
β = 95.398 (1)°Prism, colourless
V = 1790.53 (6) Å30.25 × 0.20 × 0.15 mm
Z = 8

Data collection

Bruker X8 APEXII area-detector diffractometer5229 independent reflections
Radiation source: fine-focus sealed tube3539 reflections with I > 2σ(I)
graphiteRint = 0.036
[var phi] and ω scansθmax = 30.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −30→28
Tmin = 0.396, Tmax = 0.548k = −5→5
21586 measured reflectionsl = −29→28

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) = 0.086H-atom parameters constrained
S = 1.01w = 1/[σ2(Fo2) + (0.0438P)2 + 0.1144P] where P = (Fo2 + 2Fc2)/3
5229 reflections(Δ/σ)max = 0.001
239 parametersΔρmax = 0.28 e Å3
0 restraintsΔρmin = −0.29 e Å3

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

xyzUiso*/Ueq
Br10.407800 (11)0.91753 (7)0.468246 (11)0.05023 (9)
N10.44555 (8)0.5071 (5)0.65032 (9)0.0416 (4)
N20.37942 (8)0.4903 (5)0.73723 (8)0.0400 (4)
N30.29799 (8)0.7480 (5)0.68786 (8)0.0387 (4)
N40.05385 (8)0.5642 (5)0.92033 (9)0.0400 (4)
N50.12070 (8)0.8692 (5)0.99889 (8)0.0391 (4)
N60.19961 (8)0.9449 (5)0.94033 (8)0.0373 (4)
O10.29345 (8)0.5668 (5)0.79455 (8)0.0568 (5)
O20.20597 (8)1.1650 (5)1.04514 (8)0.0576 (5)
C10.44708 (10)0.6147 (6)0.58839 (11)0.0421 (5)
H10.48260.57670.56780.050*
C20.39881 (10)0.7769 (6)0.55465 (10)0.0374 (5)
C30.34349 (10)0.8436 (5)0.58128 (10)0.0356 (5)
H30.31050.95280.55850.043*
C40.34205 (9)0.7335 (5)0.64419 (10)0.0339 (4)
C50.39361 (9)0.5704 (5)0.67562 (10)0.0345 (5)
C60.42023 (12)0.3314 (7)0.78847 (13)0.0546 (7)
H6A0.39600.22310.81880.082*
H6B0.44600.49830.81070.082*
H6C0.44550.16840.76960.082*
C70.32072 (10)0.5976 (6)0.74587 (11)0.0411 (5)
C80.23694 (10)0.8923 (7)0.67783 (13)0.0503 (6)
H8A0.22891.02140.71530.075*
H8B0.20700.71640.67130.075*
H8C0.23441.03480.64020.075*
C90.05044 (10)0.4500 (6)0.85870 (11)0.0415 (5)
H90.01490.33850.84230.050*
C100.09723 (10)0.4905 (5)0.81873 (10)0.0356 (5)
C110.15197 (9)0.6529 (5)0.83943 (10)0.0350 (5)
H110.18390.67950.81300.042*
C120.15516 (9)0.7711 (5)0.90210 (9)0.0311 (4)
C130.10513 (9)0.7226 (5)0.93943 (10)0.0337 (4)
C140.08264 (13)0.8834 (8)1.05313 (13)0.0621 (8)
H14A0.10830.86041.09330.093*
H14B0.05300.70481.04920.093*
H14C0.06151.09451.05260.093*
C150.17830 (10)1.0112 (6)0.99985 (11)0.0408 (5)
C160.25863 (10)1.0616 (6)0.92138 (12)0.0474 (6)
H16A0.28421.13180.95930.071*
H16B0.25201.24680.89190.071*
H16C0.27860.88290.90040.071*
Br20.086179 (12)0.32023 (7)0.732957 (11)0.05183 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.05040 (16)0.06094 (17)0.04140 (14)−0.00344 (12)0.01514 (11)0.00544 (11)
N10.0294 (9)0.0492 (12)0.0453 (11)0.0036 (8)−0.0008 (8)−0.0047 (8)
N20.0366 (10)0.0488 (12)0.0335 (10)0.0022 (8)−0.0025 (8)0.0032 (8)
N30.0332 (10)0.0493 (11)0.0343 (9)0.0062 (8)0.0063 (7)0.0052 (8)
N40.0318 (10)0.0484 (11)0.0403 (10)−0.0036 (8)0.0061 (8)0.0035 (8)
N50.0396 (10)0.0478 (11)0.0306 (9)0.0006 (8)0.0071 (8)−0.0029 (8)
N60.0332 (9)0.0425 (10)0.0357 (9)−0.0038 (8)0.0012 (7)0.0002 (8)
O10.0547 (10)0.0782 (13)0.0395 (9)0.0077 (9)0.0152 (8)0.0125 (8)
O20.0627 (12)0.0644 (12)0.0439 (10)−0.0092 (9)−0.0042 (9)−0.0157 (8)
C10.0303 (11)0.0507 (14)0.0463 (13)−0.0013 (10)0.0096 (10)−0.0058 (10)
C20.0362 (12)0.0429 (12)0.0337 (11)−0.0065 (10)0.0069 (9)−0.0025 (9)
C30.0322 (11)0.0394 (12)0.0350 (11)0.0000 (9)0.0015 (9)0.0010 (8)
C40.0289 (11)0.0356 (11)0.0373 (11)−0.0003 (9)0.0045 (8)−0.0016 (9)
C50.0332 (11)0.0370 (11)0.0322 (11)−0.0027 (9)−0.0028 (8)−0.0038 (8)
C60.0565 (16)0.0608 (17)0.0441 (13)0.0095 (13)−0.0084 (11)0.0098 (12)
C70.0400 (12)0.0477 (13)0.0357 (12)0.0000 (10)0.0041 (9)0.0006 (9)
C80.0385 (13)0.0615 (16)0.0520 (14)0.0104 (11)0.0101 (11)0.0106 (12)
C90.0333 (12)0.0433 (13)0.0463 (13)−0.0043 (10)−0.0046 (10)0.0021 (10)
C100.0405 (12)0.0358 (12)0.0295 (10)0.0029 (9)−0.0013 (9)0.0024 (8)
C110.0338 (11)0.0393 (12)0.0321 (11)0.0031 (9)0.0048 (8)0.0051 (8)
C120.0293 (10)0.0320 (11)0.0318 (10)0.0012 (8)0.0013 (8)0.0039 (8)
C130.0321 (11)0.0362 (11)0.0327 (10)0.0040 (9)0.0028 (8)0.0046 (8)
C140.0624 (17)0.082 (2)0.0457 (14)−0.0051 (15)0.0220 (13)−0.0141 (13)
C150.0435 (13)0.0423 (13)0.0357 (11)0.0036 (10)−0.0010 (10)0.0011 (9)
C160.0336 (12)0.0531 (14)0.0557 (15)−0.0068 (11)0.0049 (10)0.0010 (11)
Br20.06391 (18)0.05326 (16)0.03660 (13)−0.00056 (12)−0.00434 (11)−0.00705 (10)

Geometric parameters (Å, °)

Br1—C21.899 (2)C3—C41.375 (3)
N1—C51.316 (3)C3—H30.93
N1—C11.353 (3)C4—C51.404 (3)
N2—C51.376 (3)C6—H6A0.96
N2—C71.377 (3)C6—H6B0.96
N2—C61.462 (3)C6—H6C0.96
N3—C41.380 (3)C8—H8A0.96
N3—C71.390 (3)C8—H8B0.96
N3—C81.447 (3)C8—H8C0.96
N4—C131.313 (3)C9—C101.381 (3)
N4—C91.348 (3)C9—H90.93
N5—C131.374 (3)C10—C111.390 (3)
N5—C151.376 (3)C10—Br21.893 (2)
N5—C141.457 (3)C11—C121.374 (3)
N6—C121.379 (3)C11—H110.93
N6—C151.381 (3)C12—C131.407 (3)
N6—C161.456 (3)C14—H14A0.96
O1—C71.222 (3)C14—H14B0.96
O2—C151.229 (3)C14—H14C0.96
C1—C21.369 (3)C16—H16A0.96
C1—H10.93C16—H16B0.96
C2—C31.397 (3)C16—H16C0.96
C5—N1—C1114.43 (18)N2—C7—N3106.43 (18)
C5—N2—C7109.90 (17)N3—C8—H8A109.5
C5—N2—C6126.63 (19)N3—C8—H8B109.5
C7—N2—C6123.40 (19)H8A—C8—H8B109.5
C4—N3—C7109.41 (18)N3—C8—H8C109.5
C4—N3—C8127.62 (19)H8A—C8—H8C109.5
C7—N3—C8122.96 (19)H8B—C8—H8C109.5
C13—N4—C9114.63 (18)N4—C9—C10123.2 (2)
C13—N5—C15109.67 (18)N4—C9—H9118.4
C13—N5—C14126.4 (2)C10—C9—H9118.4
C15—N5—C14123.9 (2)C9—C10—C11122.1 (2)
C12—N6—C15109.26 (17)C9—C10—Br2118.81 (16)
C12—N6—C16126.73 (18)C11—C10—Br2119.06 (16)
C15—N6—C16123.92 (19)C12—C11—C10114.59 (19)
N1—C1—C2123.1 (2)C12—C11—H11122.7
N1—C1—H1118.5C10—C11—H11122.7
C2—C1—H1118.5N6—C12—C11133.1 (2)
C1—C2—C3122.7 (2)N6—C12—C13107.11 (17)
C1—C2—Br1118.44 (16)C11—C12—C13119.8 (2)
C3—C2—Br1118.88 (16)N4—C13—N5127.28 (19)
C4—C3—C2114.1 (2)N4—C13—C12125.70 (19)
C4—C3—H3122.9N5—C13—C12107.02 (18)
C2—C3—H3122.9N5—C14—H14A109.5
C3—C4—N3133.2 (2)N5—C14—H14B109.5
C3—C4—C5119.79 (19)H14A—C14—H14B109.5
N3—C4—C5107.04 (18)N5—C14—H14C109.5
N1—C5—N2126.9 (2)H14A—C14—H14C109.5
N1—C5—C4125.9 (2)H14B—C14—H14C109.5
N2—C5—C4107.22 (18)O2—C15—N6126.3 (2)
N2—C6—H6A109.5O2—C15—N5126.8 (2)
N2—C6—H6B109.5N6—C15—N5106.92 (18)
H6A—C6—H6B109.5N6—C16—H16A109.5
N2—C6—H6C109.5N6—C16—H16B109.5
H6A—C6—H6C109.5H16A—C16—H16B109.5
H6B—C6—H6C109.5N6—C16—H16C109.5
O1—C7—N2127.3 (2)H16A—C16—H16C109.5
O1—C7—N3126.3 (2)H16B—C16—H16C109.5
C5—N1—C1—C20.2 (3)C13—N4—C9—C100.9 (3)
N1—C1—C2—C3−0.4 (4)N4—C9—C10—C110.2 (3)
N1—C1—C2—Br1179.39 (17)N4—C9—C10—Br2−179.59 (17)
C1—C2—C3—C40.3 (3)C9—C10—C11—C12−0.6 (3)
Br1—C2—C3—C4−179.52 (15)Br2—C10—C11—C12179.19 (15)
C2—C3—C4—N3179.6 (2)C15—N6—C12—C11178.1 (2)
C2—C3—C4—C50.0 (3)C16—N6—C12—C111.5 (4)
C7—N3—C4—C3−179.7 (2)C15—N6—C12—C13−1.1 (2)
C8—N3—C4—C30.5 (4)C16—N6—C12—C13−177.7 (2)
C7—N3—C4—C5−0.1 (2)C10—C11—C12—N6−179.2 (2)
C8—N3—C4—C5−179.9 (2)C10—C11—C12—C13−0.1 (3)
C1—N1—C5—N2−179.9 (2)C9—N4—C13—N5178.9 (2)
C1—N1—C5—C40.1 (3)C9—N4—C13—C12−1.7 (3)
C7—N2—C5—N1180.0 (2)C15—N5—C13—N4−179.7 (2)
C6—N2—C5—N13.0 (4)C14—N5—C13—N4−1.1 (4)
C7—N2—C5—C4−0.1 (2)C15—N5—C13—C120.8 (2)
C6—N2—C5—C4−177.1 (2)C14—N5—C13—C12179.4 (2)
C3—C4—C5—N1−0.3 (3)N6—C12—C13—N4−179.3 (2)
N3—C4—C5—N1−180.0 (2)C11—C12—C13—N41.4 (3)
C3—C4—C5—N2179.80 (19)N6—C12—C13—N50.2 (2)
N3—C4—C5—N20.1 (2)C11—C12—C13—N5−179.13 (19)
C5—N2—C7—O1179.8 (2)C12—N6—C15—O2−179.2 (2)
C6—N2—C7—O1−3.1 (4)C16—N6—C15—O2−2.4 (4)
C5—N2—C7—N30.1 (3)C12—N6—C15—N51.5 (2)
C6—N2—C7—N3177.2 (2)C16—N6—C15—N5178.30 (19)
C4—N3—C7—O1−179.7 (2)C13—N5—C15—O2179.3 (2)
C8—N3—C7—O10.1 (4)C14—N5—C15—O20.6 (4)
C4—N3—C7—N20.0 (3)C13—N5—C15—N6−1.4 (2)
C8—N3—C7—N2179.8 (2)C14—N5—C15—N6179.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C8—H8C···O2i0.962.333.279 (3)167
C11—H11···O10.932.493.321 (3)148

Symmetry codes: (i) x, −y+5/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CI5119).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA..
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920-925.
  • Yutilov, Yu. M., Lopatinskaya, Kh. Ya., Smolyar, N. N. & Gres’ko, S. V. (2005). Russ. J. Org. Chem.41, 575–579.
  • Yutilov, Yu. M., Malyutina, V. F., Lopatinskaya, Kh. Ya. & Svertilova, I. A. (1998). Russ. J. Org. Chem.34, 1363–1364.

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