PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2010 April 1; 66(Pt 4): o947.
Published online 2010 March 27. doi:  10.1107/S1600536810010391
PMCID: PMC2983875

4-Benzyl-6-bromo-2-(4-methoxy­phen­yl)-4H-imidazo[4,5-b]pyridine monohydrate

Abstract

The imidazopyridine fused ring in the title compound, C20H16BrN3O·H2O, is coplanar with the aromatic ring at the 2-position [dihedral angle = 5.2 (1)°]. In the five-membered imidazo portion, the C—N bond whose C atom is also connected to the pyridine N atom has predominantly double-bond character [1.334 (2) Å] whereas the C—N bond whose atom is connected to the pyridine C atom has predominantly single-bond character [1.371 (2) Å]. The water mol­ecule engages in hydrogen bonding with the latter N atom; it is also connected to a symmetry-related water mol­ecule, generating a linear chain structure.

Related literature

For the crystal structure of 4-benzyl-6-bromo-2-phenyl-4H-imidazo[4,5-b]pyridine, see: Ouzidan et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o947-scheme1.jpg

Experimental

Crystal data

  • C20H16BrN3O·H2O
  • M r = 412.28
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o947-efi1.jpg
  • a = 10.5924 (2) Å
  • b = 5.4544 (1) Å
  • c = 31.7444 (7) Å
  • β = 100.292 (1)°
  • V = 1804.53 (6) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 2.30 mm−1
  • T = 293 K
  • 0.29 × 0.13 × 0.09 mm

Data collection

  • Bruker X8 APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.556, T max = 0.820
  • 25327 measured reflections
  • 5183 independent reflections
  • 3751 reflections with I > 2σ(I)
  • R int = 0.029

Refinement

  • R[F 2 > 2σ(F 2)] = 0.035
  • wR(F 2) = 0.098
  • S = 1.02
  • 5183 reflections
  • 244 parameters
  • 2 restraints
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.32 e Å−3
  • Δρmin = −0.38 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/S1600536810010391/pk2233sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810010391/pk2233Isup2.hkl

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

Acknowledgments

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

supplementary crystallographic information

Comment

Imidazo[4,5-b]pyridines are a class of sedative drugs. In the previous study, we reacted 6-bromo-2-phenyl-1H-imidazo[4,5-b]pyridine with benzyl chloride in the presence of a catalytic quantity of tetra-n-butylammonium bromide under mild conditions to form 4-benzyl-6-bromo-2-phenyl-4H-imidazo[4,5-b]pyridine (Ouzidan et al., 2010). The study is extended to the synthesis of the 2(4-methoxyphenyl) analog to furnish the title hydrate (Scheme I, Fig. 1). The imidazopyridine fused-ring in the C20H16BrN3O molecule is co-planar with the aromatic ring at the 2-position [dihedral angle 5.2 (1) °]. In the five-membered imidazo portion, the carbon–nitrogen bond whose carbon atom is also connected to the pyridine nitrogen atom is a double bond [1.334 (2) Å] whereas the carbon–nitrogen bond whose atom is connected to the pyridine carbon atom is a single bond [1.371 (2) Å]. The water molecule engages in hydrogen bonding with the latter nitrogen atom; it is also connected to a symmetry-related water molecule to generate a linear chain structure.

Experimental

To a solution of the 6-bromo-2-(4-methoxyphenyl)-1H-imidazo[4,5-b]pyridine (0.33 g, 1.21 mmol), potassium carbonate (0.20 g, 1.42 mmol) and tetra-n-butylammonium bromide (0.04 g (0,1 mmol) in DMF (15 ml) was added benzyl chloride (0.15 ml, 1.31 mmol). Stirring was continued at room temperature for 12 hours. The salt was removed by filtration and the filtrate concentrated under reduced pressure. The residue was chromatographed on a column of silica gel with ethyl acetate/hexane (1/1) as eluent. Yellow crystals were isolated when the solvent was allowed to evaporate.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93–0.97 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The water H-atoms were located in a difference Fourier map, and were refined with a distance restraint of O–H 0.84 (1) Å.

Figures

Fig. 1.
Thermal ellipsoid plot (Barbour, 2001) of C20H16BrN3O.H2O at the 50% probability level; hydrogen atoms are drawn as spheres of arbitrary radius.

Crystal data

C20H16BrN3O·H2OF(000) = 840
Mr = 412.28Dx = 1.518 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 6654 reflections
a = 10.5924 (2) Åθ = 3.0–28.2°
b = 5.4544 (1) ŵ = 2.30 mm1
c = 31.7444 (7) ÅT = 293 K
β = 100.292 (1)°Prism, yellow
V = 1804.53 (6) Å30.29 × 0.13 × 0.09 mm
Z = 4

Data collection

Bruker X8 APEXII diffractometer5183 independent reflections
Radiation source: fine-focus sealed tube3751 reflections with I > 2σ(I)
graphiteRint = 0.029
[var phi] and ω scansθmax = 29.8°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −14→14
Tmin = 0.556, Tmax = 0.820k = −7→7
25327 measured reflectionsl = −40→44

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)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.098H atoms treated by a mixture of independent and constrained refinement
S = 1.02w = 1/[σ2(Fo2) + (0.0469P)2 + 0.4879P] where P = (Fo2 + 2Fc2)/3
5183 reflections(Δ/σ)max = 0.001
244 parametersΔρmax = 0.32 e Å3
2 restraintsΔρmin = −0.38 e Å3

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

xyzUiso*/Ueq
Br10.33516 (2)0.25313 (4)0.229786 (7)0.06505 (10)
O1W0.0347 (2)1.0524 (4)0.27301 (7)0.0809 (5)
H110.091 (3)1.063 (10)0.2955 (9)0.18 (2)*
H120.032 (5)1.199 (4)0.2641 (17)0.16 (2)*
N10.49030 (13)0.4485 (3)0.35254 (4)0.0370 (3)
N20.25772 (13)0.9195 (3)0.34637 (4)0.0397 (3)
N30.43173 (14)0.7798 (2)0.39573 (5)0.0368 (3)
O10.24437 (17)1.6309 (3)0.50907 (5)0.0663 (4)
C10.36408 (17)0.4170 (3)0.28302 (5)0.0437 (4)
C20.28596 (17)0.6138 (4)0.28937 (5)0.0438 (4)
H20.21930.66660.26820.053*
C30.31304 (16)0.7260 (3)0.32892 (6)0.0380 (4)
C40.41915 (15)0.6437 (3)0.36032 (5)0.0351 (3)
C50.46265 (17)0.3344 (3)0.31392 (6)0.0417 (4)
H50.51080.19950.30840.050*
C60.33092 (15)0.9407 (3)0.38565 (5)0.0355 (3)
C70.30567 (16)1.1232 (3)0.41692 (5)0.0374 (3)
C80.20011 (19)1.2782 (3)0.40877 (6)0.0466 (4)
H80.14461.26780.38260.056*
C90.17580 (19)1.4476 (4)0.43868 (6)0.0501 (5)
H90.10411.54850.43270.060*
C100.25837 (19)1.4669 (3)0.47759 (6)0.0462 (4)
C110.3644 (2)1.3137 (4)0.48642 (6)0.0501 (5)
H11A0.41971.32460.51260.060*
C120.38781 (18)1.1462 (4)0.45650 (5)0.0448 (4)
H12A0.45971.04580.46260.054*
C130.1389 (3)1.7962 (4)0.50100 (10)0.0722 (7)
H13A0.14241.90560.52490.108*
H13B0.06011.70540.49710.108*
H13C0.14311.88910.47560.108*
C140.60115 (17)0.3669 (3)0.38527 (6)0.0409 (4)
H14A0.60950.19010.38390.049*
H14B0.58560.40910.41360.049*
C150.72405 (16)0.4858 (3)0.37807 (5)0.0376 (4)
C160.76570 (19)0.7021 (3)0.39913 (6)0.0460 (4)
H160.71940.77030.41850.055*
C170.8757 (2)0.8163 (4)0.39140 (8)0.0592 (5)
H170.90330.96070.40570.071*
C180.9443 (2)0.7187 (5)0.36287 (8)0.0675 (7)
H181.01740.79830.35740.081*
C190.9054 (2)0.5027 (5)0.34216 (7)0.0644 (7)
H190.95290.43560.32300.077*
C200.79559 (18)0.3847 (4)0.34969 (6)0.0495 (5)
H200.76980.23820.33580.059*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.06531 (16)0.07264 (17)0.05167 (13)0.00232 (11)−0.00455 (10)−0.02553 (10)
O1W0.0702 (12)0.0877 (14)0.0805 (13)−0.0048 (10)0.0017 (10)0.0014 (11)
N10.0327 (7)0.0387 (7)0.0383 (7)−0.0010 (6)0.0027 (5)0.0004 (6)
N20.0325 (7)0.0490 (8)0.0361 (7)0.0033 (6)0.0020 (5)0.0001 (6)
N30.0330 (7)0.0413 (8)0.0349 (7)0.0013 (6)0.0024 (5)0.0003 (5)
O10.0887 (11)0.0604 (9)0.0474 (8)0.0241 (9)0.0063 (7)−0.0108 (7)
C10.0387 (9)0.0493 (10)0.0411 (8)−0.0084 (8)0.0018 (7)−0.0091 (7)
C20.0340 (9)0.0543 (11)0.0402 (8)−0.0023 (8)−0.0016 (7)−0.0028 (8)
C30.0296 (8)0.0457 (10)0.0375 (8)−0.0033 (7)0.0025 (6)0.0006 (7)
C40.0292 (8)0.0397 (8)0.0357 (8)−0.0028 (7)0.0041 (6)0.0022 (6)
C50.0388 (9)0.0396 (9)0.0460 (9)−0.0031 (7)0.0061 (7)−0.0059 (7)
C60.0307 (8)0.0414 (9)0.0340 (7)−0.0010 (7)0.0044 (6)0.0027 (6)
C70.0354 (8)0.0419 (9)0.0343 (8)0.0007 (7)0.0049 (6)0.0026 (7)
C80.0423 (10)0.0532 (11)0.0407 (9)0.0102 (8)−0.0019 (7)−0.0005 (7)
C90.0486 (11)0.0530 (11)0.0469 (10)0.0175 (9)0.0036 (8)0.0006 (8)
C100.0568 (11)0.0437 (10)0.0382 (8)0.0056 (8)0.0090 (8)0.0002 (7)
C110.0555 (11)0.0559 (11)0.0347 (9)0.0090 (9)−0.0035 (8)−0.0017 (8)
C120.0424 (10)0.0513 (10)0.0380 (8)0.0099 (8)0.0000 (7)0.0035 (8)
C130.0841 (18)0.0593 (14)0.0763 (17)0.0176 (12)0.0229 (14)−0.0141 (12)
C140.0414 (9)0.0387 (9)0.0406 (8)0.0037 (7)0.0015 (7)0.0072 (7)
C150.0337 (8)0.0409 (9)0.0359 (8)0.0094 (7)−0.0001 (6)0.0084 (6)
C160.0436 (10)0.0443 (10)0.0477 (10)0.0036 (8)0.0020 (8)0.0036 (7)
C170.0487 (12)0.0578 (12)0.0652 (13)−0.0073 (10)−0.0060 (10)0.0126 (10)
C180.0383 (11)0.097 (2)0.0640 (14)−0.0018 (11)−0.0006 (10)0.0325 (13)
C190.0426 (11)0.107 (2)0.0454 (10)0.0293 (12)0.0118 (9)0.0190 (12)
C200.0471 (11)0.0600 (12)0.0386 (9)0.0204 (9)0.0006 (8)0.0025 (8)

Geometric parameters (Å, °)

Br1—C11.8877 (17)C9—C101.384 (3)
O1w—H110.85 (1)C9—H90.9300
O1w—H120.85 (1)C10—C111.388 (3)
N1—C41.352 (2)C11—C121.372 (3)
N1—C51.359 (2)C11—H11A0.9300
N1—C141.490 (2)C12—H12A0.9300
N2—C61.351 (2)C13—H13A0.9600
N2—C31.371 (2)C13—H13B0.9600
N3—C41.334 (2)C13—H13C0.9600
N3—C61.375 (2)C14—C151.508 (2)
O1—C101.369 (2)C14—H14A0.9700
O1—C131.423 (3)C14—H14B0.9700
C1—C51.374 (3)C15—C161.389 (3)
C1—C21.392 (3)C15—C201.390 (3)
C2—C31.380 (2)C16—C171.381 (3)
C2—H20.9300C16—H160.9300
C3—C41.435 (2)C17—C181.366 (4)
C5—H50.9300C17—H170.9300
C6—C71.464 (2)C18—C191.376 (4)
C7—C81.389 (2)C18—H180.9300
C7—C121.400 (2)C19—C201.387 (3)
C8—C91.382 (3)C19—H190.9300
C8—H80.9300C20—H200.9300
H11—O1W—H12101 (5)C12—C11—C10120.05 (17)
C4—N1—C5119.19 (14)C12—C11—H11A120.0
C4—N1—C14120.23 (14)C10—C11—H11A120.0
C5—N1—C14120.53 (15)C11—C12—C7121.39 (17)
C6—N2—C3102.87 (13)C11—C12—H12A119.3
C4—N3—C6101.69 (13)C7—C12—H12A119.3
C10—O1—C13117.82 (18)O1—C13—H13A109.5
C5—C1—C2123.00 (16)O1—C13—H13B109.5
C5—C1—Br1117.70 (14)H13A—C13—H13B109.5
C2—C1—Br1119.29 (13)O1—C13—H13C109.5
C3—C2—C1116.21 (16)H13A—C13—H13C109.5
C3—C2—H2121.9H13B—C13—H13C109.5
C1—C2—H2121.9N1—C14—C15111.09 (13)
N2—C3—C2132.43 (16)N1—C14—H14A109.4
N2—C3—C4107.37 (14)C15—C14—H14A109.4
C2—C3—C4120.19 (16)N1—C14—H14B109.4
N3—C4—N1128.09 (14)C15—C14—H14B109.4
N3—C4—C3111.05 (15)H14A—C14—H14B108.0
N1—C4—C3120.84 (15)C16—C15—C20119.06 (18)
N1—C5—C1120.50 (17)C16—C15—C14120.06 (16)
N1—C5—H5119.8C20—C15—C14120.86 (17)
C1—C5—H5119.8C17—C16—C15120.2 (2)
N2—C6—N3116.99 (15)C17—C16—H16119.9
N2—C6—C7122.69 (15)C15—C16—H16119.9
N3—C6—C7120.31 (14)C18—C17—C16120.5 (2)
C8—C7—C12117.59 (16)C18—C17—H17119.8
C8—C7—C6121.75 (15)C16—C17—H17119.8
C12—C7—C6120.66 (15)C17—C18—C19120.1 (2)
C9—C8—C7121.45 (17)C17—C18—H18120.0
C9—C8—H8119.3C19—C18—H18120.0
C7—C8—H8119.3C18—C19—C20120.3 (2)
C8—C9—C10119.90 (17)C18—C19—H19119.9
C8—C9—H9120.0C20—C19—H19119.9
C10—C9—H9120.0C19—C20—C15119.9 (2)
O1—C10—C9124.58 (17)C19—C20—H20120.0
O1—C10—C11115.81 (17)C15—C20—H20120.0
C9—C10—C11119.61 (17)
C5—C1—C2—C30.4 (3)N2—C6—C7—C12−176.91 (17)
Br1—C1—C2—C3−179.58 (13)N3—C6—C7—C123.7 (2)
C6—N2—C3—C2−178.68 (19)C12—C7—C8—C9−0.7 (3)
C6—N2—C3—C4−0.05 (18)C6—C7—C8—C9179.03 (18)
C1—C2—C3—N2−179.63 (18)C7—C8—C9—C100.7 (3)
C1—C2—C3—C41.9 (3)C13—O1—C10—C9−1.2 (3)
C6—N3—C4—N1−177.47 (17)C13—O1—C10—C11178.4 (2)
C6—N3—C4—C31.19 (18)C8—C9—C10—O1178.8 (2)
C5—N1—C4—N3−179.48 (17)C8—C9—C10—C11−0.7 (3)
C14—N1—C4—N3−2.2 (3)O1—C10—C11—C12−178.8 (2)
C5—N1—C4—C32.0 (2)C9—C10—C11—C120.7 (3)
C14—N1—C4—C3179.30 (15)C10—C11—C12—C7−0.8 (3)
N2—C3—C4—N3−0.77 (19)C8—C7—C12—C110.7 (3)
C2—C3—C4—N3178.06 (16)C6—C7—C12—C11−178.99 (18)
N2—C3—C4—N1178.00 (15)C4—N1—C14—C15−92.30 (18)
C2—C3—C4—N1−3.2 (3)C5—N1—C14—C1584.99 (19)
C4—N1—C5—C10.3 (3)N1—C14—C15—C1693.17 (18)
C14—N1—C5—C1−176.98 (16)N1—C14—C15—C20−85.35 (19)
C2—C1—C5—N1−1.6 (3)C20—C15—C16—C170.9 (3)
Br1—C1—C5—N1178.39 (13)C14—C15—C16—C17−177.60 (17)
C3—N2—C6—N30.88 (19)C15—C16—C17—C180.3 (3)
C3—N2—C6—C7−178.50 (15)C16—C17—C18—C19−1.2 (3)
C4—N3—C6—N2−1.33 (19)C17—C18—C19—C200.8 (3)
C4—N3—C6—C7178.06 (15)C18—C19—C20—C150.4 (3)
N2—C6—C7—C83.4 (3)C16—C15—C20—C19−1.3 (2)
N3—C6—C7—C8−175.95 (17)C14—C15—C20—C19177.23 (15)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O1w—H11···N20.85 (1)2.30 (2)3.092 (3)155 (5)
O1w—H12···O1Wi0.85 (1)2.30 (2)3.119 (2)162 (5)

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: PK2233).

References

  • Barbour, L. J. (2001). J. Supramol. Chem.1, 189–191.
  • Bruker (2008). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Ouzidan, Y., Kandri Rodi, Y., Obbade, S., Essassi, E. M. & Ng, S. W. (2010). Acta Cryst. E66, o947. [PMC free article] [PubMed]
  • 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