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access6-Bromo-3-methyl-2-phenyl-3H-imidazo[4,5-b]pyridine
aLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Immouzzer, BP 2202 Fès, Morocco, bLaboratoire de Chimie Organique Hétérocyclique URAC21, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco, cDepartamento de Quimica Inorganica y Organica, ESTCE, Universitat Jaume I, E-12080 Castellon, Spain, dInstitut für Anorganische Chemie, J. W. Goethe-Universität Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, Germany, and eLaboratoire de Chimie du Solide Appliquée, Faculté des Sciences, Université Mohammed V-Agdal, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
*Correspondence e-mail: ouzidan@yahoo.fr
The two fused five- and six-membered rings building the molecule of the title compound, C13H10BrN3, are approximately planar, the largest deviation from the mean plane being 0.004 (2) Å. The dihedral angle between the imidazo[4,5-b]pyridine mean plane and that of the phenyl ring is 41.84 (11)°. The structure is held together by slipped π–π stacking between symmetry-related molecules, with an interplanar distance of 3.583 (1) Å and a centroid–centroid vector of 3.670 (2) Å.
Related literature
For background regarding biological activity of imidazo[4,5-b]pyridines, see: Cristalli et al. (1995![[Cristalli, G., Vittori, S., Eleuteri, A., Volpini, R., Camaioni, E., Lupidi, G., Mahmood, N., Bevilacqua, F. & Palu, G. (1995). J. Med. Chem. 38, 4019-4025.]](../../../../../../logos/arrows/e_arr.gif "Cristalli, G., Vittori, S., Eleuteri, A., Volpini, R., Camaioni, E., Lupidi, G., Mahmood, N., Bevilacqua, F. & Palu, G. (1995). J. Med. Chem. 38, 4019-4025.")
); Bukowski & Kaliszan (1991); Aridoss et al. (2006); Bavetsias et al. (2007). For background to their pharmacological activity, see: Chen & Dost (1992); Weier et al. (1993).
![[Scheme 1]](dn2697scheme1.gif)
Experimental
Crystal data
|
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks I, global. DOI: 10.1107/S1600536811022318/dn2697sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536811022318/dn2697Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536811022318/dn2697Isup3.cml
To a solution of the 6-bromo-2-phenyl-1H-imidazo[4,5-b]pyridine (0.3 g, 1.09 mmol), potassium carbonate (0.2 g, 1.42 mmol) and tetra-n-butylammonium bromide (0.04 g, 0.1 mmol) in DMF (15 ml) was added methyl iodide (0.08 ml, 1.31 mmol). Stirring was continued at room temperature for 12 h. The salt was removed by filtration and the filtrate concentrated under reduced pressure. The residue was separated by on a column of silica gel with ethyl acetate/hexane (1/2) as The compound was recrystallized from ethanol.
H atoms were located in a difference map and treated as riding with C—H = 0.93 Å, and 0.96 Å for aromatic and methyl respectively and with Uiso(H) = 1.2 Ueq (aromatic) and Uiso(H) = 1.5 Ueq(methyl).
Data collection: SMART (Bruker, 1997); cell SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./dn2697fig1thm.gif) | Fig. 1. : Molecular view of the title compound with the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are represented as small circles of arbitrary radii. |
| C13H10BrN3 | F(000) = 1152 |
| Mr = 288.15 | Dx = 1.643 Mg m−3 |
| Orthorhombic, Pbca | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ac 2ab | Cell parameters from 5157 reflections |
| a = 13.7138 (4) Å | θ = 3.0–29.6° |
| b = 6.7088 (2) Å | µ = 3.51 mm−1 |
| c = 25.3217 (7) Å | T = 298 K |
| V = 2329.68 (12) Å3 | Platelet, colourless |
| Z = 8 | 0.60 × 0.30 × 0.06 mm |
| Bruker CCD three-circle diffractometer | 2378 independent reflections |
| Radiation source: fine-focus sealed tube | 1804 reflections with I > 2σ(I) |
| Graphite monochromator | Rint = 0.047 |
| ω scans | θmax = 26.4°, θmin = 2.2° |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | h = 0→17 |
| Tmin = 0.227, Tmax = 0.825 | k = 0→8 |
| 13535 measured reflections | l = 0→31 |
| 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)] = 0.033 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.04 | w = 1/[σ2(Fo2) + (0.0361P)2 + 1.2509P] where P = (Fo2 + 2Fc2)/3 |
| 2378 reflections | (Δ/σ)max = 0.002 |
| 155 parameters | Δρmax = 0.37 e Å−3 |
| 0 restraints | Δρmin = −0.40 e Å−3 |
| C13H10BrN3 | V = 2329.68 (12) Å3 |
| Mr = 288.15 | Z = 8 |
| Orthorhombic, Pbca | Mo Kα radiation |
| a = 13.7138 (4) Å | µ = 3.51 mm−1 |
| b = 6.7088 (2) Å | T = 298 K |
| c = 25.3217 (7) Å | 0.60 × 0.30 × 0.06 mm |
| Bruker CCD three-circle diffractometer | 2378 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 1997) | 1804 reflections with I > 2σ(I) |
| Tmin = 0.227, Tmax = 0.825 | Rint = 0.047 |
| 13535 measured reflections |
| R[F2 > 2σ(F2)] = 0.033 | 0 restraints |
| wR(F2) = 0.090 | H-atom parameters constrained |
| S = 1.04 | Δρmax = 0.37 e Å−3 |
| 2378 reflections | Δρmin = −0.40 e Å−3 |
| 155 parameters |
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. |
Refinement. Refinement of F2 against all reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on all data will be even larger. |
| x | y | z | Uiso*/Ueq | ||
| Br1 | 0.65259 (2) | 1.16657 (6) | 0.626463 (10) | 0.06788 (15) | |
| N1 | 0.60483 (17) | 0.7251 (3) | 0.51723 (8) | 0.0509 (6) | |
| N2 | 0.60942 (14) | 0.7570 (3) | 0.42245 (7) | 0.0396 (4) | |
| N3 | 0.64274 (15) | 1.0833 (3) | 0.41558 (8) | 0.0425 (5) | |
| C1 | 0.6160 (2) | 0.8347 (4) | 0.56091 (10) | 0.0528 (7) | |
| H1 | 0.6093 | 0.7719 | 0.5934 | 0.063* | |
| C2 | 0.63682 (17) | 1.0361 (4) | 0.56042 (9) | 0.0477 (6) | |
| C3 | 0.64811 (18) | 1.1434 (4) | 0.51422 (10) | 0.0464 (6) | |
| H3 | 0.6620 | 1.2790 | 0.5138 | 0.056* | |
| C4 | 0.63692 (16) | 1.0313 (4) | 0.46819 (9) | 0.0385 (5) | |
| C5 | 0.61634 (17) | 0.8291 (3) | 0.47310 (9) | 0.0386 (5) | |
| C6 | 0.62568 (16) | 0.9162 (4) | 0.38966 (9) | 0.0369 (5) | |
| C7 | 0.62409 (16) | 0.9055 (4) | 0.33165 (9) | 0.0378 (5) | |
| C8 | 0.58108 (18) | 1.0590 (4) | 0.30370 (9) | 0.0463 (6) | |
| H8 | 0.5525 | 1.1644 | 0.3218 | 0.056* | |
| C9 | 0.5801 (2) | 1.0574 (5) | 0.24902 (10) | 0.0561 (7) | |
| H9 | 0.5506 | 1.1610 | 0.2306 | 0.067* | |
| C10 | 0.6226 (2) | 0.9037 (5) | 0.22203 (11) | 0.0590 (8) | |
| H10 | 0.6217 | 0.9025 | 0.1853 | 0.071* | |
| C11 | 0.6665 (2) | 0.7515 (6) | 0.24919 (12) | 0.0641 (8) | |
| H11 | 0.6957 | 0.6476 | 0.2307 | 0.077* | |
| C12 | 0.66776 (19) | 0.7512 (5) | 0.30402 (11) | 0.0531 (7) | |
| H12 | 0.6978 | 0.6475 | 0.3222 | 0.064* | |
| C13 | 0.5829 (2) | 0.5528 (4) | 0.40922 (12) | 0.0607 (8) | |
| H13A | 0.5461 | 0.5518 | 0.3770 | 0.091* | |
| H13B | 0.5441 | 0.4973 | 0.4372 | 0.091* | |
| H13C | 0.6409 | 0.4746 | 0.4048 | 0.091* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Br1 | 0.0669 (2) | 0.0970 (3) | 0.03975 (18) | −0.00449 (16) | −0.00264 (12) | −0.01196 (14) |
| N1 | 0.0583 (14) | 0.0484 (13) | 0.0460 (12) | −0.0094 (11) | −0.0071 (10) | 0.0159 (10) |
| N2 | 0.0467 (11) | 0.0275 (10) | 0.0445 (11) | −0.0009 (9) | −0.0056 (9) | 0.0035 (9) |
| N3 | 0.0584 (13) | 0.0312 (10) | 0.0379 (10) | −0.0030 (9) | 0.0000 (9) | 0.0023 (9) |
| C1 | 0.0529 (15) | 0.0641 (19) | 0.0414 (14) | −0.0091 (14) | −0.0064 (11) | 0.0176 (13) |
| C2 | 0.0411 (13) | 0.0662 (19) | 0.0358 (12) | −0.0012 (12) | −0.0042 (10) | 0.0006 (12) |
| C3 | 0.0526 (15) | 0.0436 (15) | 0.0430 (13) | −0.0035 (11) | −0.0023 (11) | −0.0017 (11) |
| C4 | 0.0427 (13) | 0.0344 (13) | 0.0385 (12) | −0.0008 (10) | −0.0019 (9) | 0.0043 (10) |
| C5 | 0.0385 (12) | 0.0347 (12) | 0.0426 (12) | −0.0022 (10) | −0.0061 (10) | 0.0066 (10) |
| C6 | 0.0381 (12) | 0.0316 (12) | 0.0410 (12) | 0.0030 (10) | −0.0028 (10) | 0.0016 (10) |
| C7 | 0.0362 (11) | 0.0391 (13) | 0.0380 (12) | −0.0019 (10) | 0.0003 (9) | −0.0014 (10) |
| C8 | 0.0522 (14) | 0.0459 (15) | 0.0408 (13) | 0.0073 (12) | 0.0051 (11) | 0.0026 (11) |
| C9 | 0.0575 (16) | 0.071 (2) | 0.0402 (14) | 0.0032 (14) | 0.0022 (12) | 0.0109 (13) |
| C10 | 0.0541 (15) | 0.084 (2) | 0.0389 (14) | −0.0069 (16) | 0.0070 (12) | −0.0068 (14) |
| C11 | 0.0615 (19) | 0.071 (2) | 0.0594 (18) | 0.0084 (16) | 0.0145 (14) | −0.0249 (17) |
| C12 | 0.0514 (16) | 0.0528 (16) | 0.0551 (16) | 0.0114 (13) | 0.0018 (12) | −0.0064 (14) |
| C13 | 0.087 (2) | 0.0329 (14) | 0.0622 (17) | −0.0136 (14) | −0.0098 (15) | −0.0003 (13) |
| Br1—C2 | 1.900 (3) | C7—C8 | 1.382 (3) |
| N1—C5 | 1.327 (3) | C7—C12 | 1.386 (4) |
| N1—C1 | 1.337 (3) | C8—C9 | 1.385 (3) |
| N2—C6 | 1.371 (3) | C8—H8 | 0.9300 |
| N2—C5 | 1.374 (3) | C9—C10 | 1.367 (4) |
| N2—C13 | 1.456 (3) | C9—H9 | 0.9300 |
| N3—C6 | 1.320 (3) | C10—C11 | 1.371 (5) |
| N3—C4 | 1.380 (3) | C10—H10 | 0.9300 |
| C1—C2 | 1.381 (4) | C11—C12 | 1.388 (4) |
| C1—H1 | 0.9300 | C11—H11 | 0.9300 |
| C2—C3 | 1.382 (4) | C12—H12 | 0.9300 |
| C3—C4 | 1.395 (3) | C13—H13A | 0.9600 |
| C3—H3 | 0.9300 | C13—H13B | 0.9600 |
| C4—C5 | 1.391 (3) | C13—H13C | 0.9600 |
| C6—C7 | 1.471 (3) | ||
| C5—N1—C1 | 113.2 (2) | C8—C7—C6 | 118.8 (2) |
| C6—N2—C5 | 106.23 (19) | C12—C7—C6 | 122.3 (2) |
| C6—N2—C13 | 129.4 (2) | C7—C8—C9 | 120.7 (3) |
| C5—N2—C13 | 124.3 (2) | C7—C8—H8 | 119.7 |
| C6—N3—C4 | 104.8 (2) | C9—C8—H8 | 119.7 |
| N1—C1—C2 | 123.7 (2) | C10—C9—C8 | 120.1 (3) |
| N1—C1—H1 | 118.2 | C10—C9—H9 | 119.9 |
| C2—C1—H1 | 118.2 | C8—C9—H9 | 119.9 |
| C1—C2—C3 | 122.7 (2) | C9—C10—C11 | 119.9 (3) |
| C1—C2—Br1 | 117.80 (19) | C9—C10—H10 | 120.1 |
| C3—C2—Br1 | 119.5 (2) | C11—C10—H10 | 120.1 |
| C2—C3—C4 | 114.5 (2) | C10—C11—C12 | 120.6 (3) |
| C2—C3—H3 | 122.8 | C10—C11—H11 | 119.7 |
| C4—C3—H3 | 122.8 | C12—C11—H11 | 119.7 |
| N3—C4—C5 | 110.2 (2) | C7—C12—C11 | 119.9 (3) |
| N3—C4—C3 | 131.6 (2) | C7—C12—H12 | 120.1 |
| C5—C4—C3 | 118.2 (2) | C11—C12—H12 | 120.1 |
| N1—C5—N2 | 126.4 (2) | N2—C13—H13A | 109.5 |
| N1—C5—C4 | 127.7 (2) | N2—C13—H13B | 109.5 |
| N2—C5—C4 | 105.9 (2) | H13A—C13—H13B | 109.5 |
| N3—C6—N2 | 112.9 (2) | N2—C13—H13C | 109.5 |
| N3—C6—C7 | 122.7 (2) | H13A—C13—H13C | 109.5 |
| N2—C6—C7 | 124.3 (2) | H13B—C13—H13C | 109.5 |
| C8—C7—C12 | 118.9 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C13H10BrN3 |
| Mr | 288.15 |
| Crystal system, space group | Orthorhombic, Pbca |
| Temperature (K) | 298 |
| a, b, c (Å) | 13.7138 (4), 6.7088 (2), 25.3217 (7) |
| V (Å3) | 2329.68 (12) |
| Z | 8 |
| Radiation type | Mo Kα |
| µ (mm−1) | 3.51 |
| Crystal size (mm) | 0.60 × 0.30 × 0.06 |
| Data collection | |
| Diffractometer | Bruker CCD three-circle diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 1997) |
| Tmin, Tmax | 0.227, 0.825 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 13535, 2378, 1804 |
| Rint | 0.047 |
| (sin θ/λ)max (Å−1) | 0.625 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.033, 0.090, 1.04 |
| No. of reflections | 2378 |
| No. of parameters | 155 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.37, −0.40 |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
References
Aridoss, G., Balasubramanian, S., Parthiban, P. & Kabilan, S. (2006). Eur. J. Med. Chem. 41, 268–275. Web of Science CrossRef PubMed CAS Google Scholar
Bavetsias, V., Sun, C., Bouloc, N., Reynisson, J., Workman, P., Linardopoulos, S. & McDonald, E. (2007). Bioorg. Med. Chem. Lett. 17, 6567–6571. Web of Science CrossRef PubMed CAS Google Scholar
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bukowski, L. & Kaliszan, R. (1991). Arch. Pharm. 324, 121–127. CrossRef CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
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Cristalli, G., Vittori, S., Eleuteri, A., Volpini, R., Camaioni, E., Lupidi, G., Mahmood, N., Bevilacqua, F. & Palu, G. (1995). J. Med. Chem. 38, 4019–4025. CrossRef CAS PubMed Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
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Heterocyclic ring systems having imidazo[4,5-b]pyridine nucleus can be considered as structural analogues of purines and have shown a diverse biological activity depending on the substituents of the heterocyclic ring. Their activity includes antiviral (Cristalli et al., 1995), anticancer (Bavetsias et al., 2007), tituberculostatic (Bukowski & Kaliszan, 1991) and antimitotic (Aridoss et al., 2006) actions. They have also been evaluated as antagonists of various biological receptors including angiotensin-II (Chen & Dost, 1992) and platelet activating factor (PAF) (Weier et al., 1993). Hence, the synthesis of imidazo[4,5-b]pyridine derivatives represents nowadays an important topic in organic synthesis.
The two fused five and six-membered rings are nearly planar with the maximum deviation of 0.004 (2) Å from N1. The dihedral angle between the imidazo[4,5-b]pyridine system and the phenyl ring is 41.84 (11)° (Fig. 1). The structure is held together by slipped π-π stacking between symmetry related molecules with interplanar distance of 3.583 (1) Å and centroid to centroid vector of 3.670 (2) Å resulting in a slippage of 0.79 Å.