3-Benzyl-6-bromo-2-(2-fur­yl)-3H-imidazo[4,5-b]pyridine

Ouzidan, Y.; Rodi, Y.K.; Zouihri, H.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S160053681002475X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 7| July 2010| Page o1874

doi:10.1107/S160053681002475X

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3-Benzyl-6-bromo-2-(2-furyl)-3H-imidazo[4,5-b]pyridine

Younès Ouzidan,^a Youssef Kandri Rodi,^a Hafid Zouihri,^b El Mokhtar Essassi ^c and Seik Weng Ng ^d ^*

^aLaboratoire de Chimie Organique Appliquée, Faculté des Sciences et Techniques, Université Sidi Mohamed Ben Abdallah, Fès, Morocco, ^bCNRST Division UATRS, Angle Allal Fassi/FAR, BP 8027 Hay Riad, Rabat, Morocco, ^cLaboratoire de Chimie Organique Hétérocyclique, Pôle de Compétences Pharmacochimie, Université Mohammed V-Agdal, BP 1014 Avenue Ibn Batout, Rabat, Morocco, and ^dDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: seikweng@um.edu.my

(Received 23 June 2010; accepted 24 June 2010; online 30 June 2010)

In the title molecule, C₁₇H₁₂BrN₃O, the imidazopyridine ring system is almost coplanar with the furan ring [dihedral angle = 2.0 (3)°]. The benzyl phenyl ring is oriented at dihedral angles of 85.2 (2) and 85.5 (1)°, respectively, with respect to the furan ring and the imidazopyridine ring system. In the crystal, molecules are linked into chains propagating along the b axis by C—H⋯N hydrogen bonds. Adjacent chains are linked via short Br⋯Br contacts [3.493 (1) Å].

Related literature

For a related structure, see: Ouzidan et al. (2010 ).

Experimental

Crystal data

C₁₇H₁₂BrN₃O
M_r = 354.21
Monoclinic, P 2₁ /c
a = 15.8422 (3) Å
b = 5.4747 (1) Å
c = 18.4243 (3) Å
β = 111.509 (1)°
V = 1486.68 (5) Å³
Z = 4
Mo Kα radiation
μ = 2.77 mm⁻¹
T = 293 K
0.25 × 0.25 × 0.10 mm

Data collection

Bruker X8 APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.544, T_max = 0.769
19471 measured reflections
2614 independent reflections
2105 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.110
S = 0.97
2614 reflections
199 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯N3ⁱ	0.93	2.51	3.399 (4)	160
Symmetry code: (i) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681002475X/ci5113sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681002475X/ci5113Isup2.hkl

checkCIF report

Comment top

The imidazo[4,5-b]pyridine unit is an important heterocyclic nucleus found in a large number of molecules in medicinal chemistry. Heterocycles derived from such compounds posess useful medicinal properties. Owing to their importance, strategies have been developed for their synthesis. The most popular synthetic approach involves the cyclocondensation of 2,3-pyridinediamine with carboxylic acid derivatives or on condensation with aldehydes. An earlier study reported the crystal structure of 4-benzyl-6-bromo-2-phenyl-4H-imidazo[4,5-b]pyridine (Ouzidan et al., 2010), which was synthesized by using a much more convenient route. The synthesis is extended to the title compound.

In the title molecule (Scheme and Fig. 1), the imidazopyridine ring system is almost coplanar with the furan ring at the 2-position of the five-membered ring [dihedral angle = 2.0 (3) °]. The molecules are linked into chains along the b axis by C—H···N hydrogen bonds (Table 1). The adjacent chains are linked via short Br···Br contacts [3.493 (1) Å].

Related literature top

For a related structure, see: Ouzidan et al. (2010).

Experimental top

6-Bromo-2-furyl-3H-imidazo[4,5-b]pyridine (0.30 g, 1.13 mmol) was dissolved in DMF (15 ml). Potassium carbonate (0.2 g, 1,48 mmol), tetra-n-butylammonium bromide (0.04 g, 0.1 mmol) and benzyl chloride (0.15 ml, 1.36 mmol) were added. Stirring was continued at room temperature for 12 h. The mixture was filtered and the solvent removed under reduced pressure. The residue was chromatographed on a column of silica gel with ethyl acetate-hexane (1/2) as eluent. The compound was recrystallized from chloroform to give orange crystals.

Computing details top

Data collection: APEX2 (Bruker, 2008); cell refinement: SAINT (Bruker, 2008); data reduction: SAINT (Bruker, 2008); 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).

Figures top

Fig. 1. Displacement ellipsoid plot (Barbour, 2001) of the molecule of C₁₇H₁₂BrN₃O at the 50% probability level. H atoms are shown as spheres of arbitrary radii.

3-Benzyl-6-bromo-2-(2-furyl)-3H-imidazo[4,5-b]pyridine top

Crystal data top

C₁₇H₁₂BrN₃O	F(000) = 712
M_r = 354.21	D_x = 1.583 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5830 reflections
a = 15.8422 (3) Å	θ = 2.7–23.3°
b = 5.4747 (1) Å	µ = 2.77 mm⁻¹
c = 18.4243 (3) Å	T = 293 K
β = 111.509 (1)°	Prism, orange
V = 1486.68 (5) Å³	0.25 × 0.25 × 0.10 mm
Z = 4

Data collection top

Bruker X8 APEXII area-detector diffractometer	2614 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −17→18
T_min = 0.544, T_max = 0.769	k = −6→5
19471 measured reflections	l = −21→18

Refinement top

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) = 0.110	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0848P)² + 0.0891P] where P = (F_o² + 2F_c²)/3
2614 reflections	(Δ/σ)_max = 0.001
199 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.44 e Å⁻³

Crystal data top

C₁₇H₁₂BrN₃O	V = 1486.68 (5) Å³
M_r = 354.21	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 15.8422 (3) Å	µ = 2.77 mm⁻¹
b = 5.4747 (1) Å	T = 293 K
c = 18.4243 (3) Å	0.25 × 0.25 × 0.10 mm
β = 111.509 (1)°

Data collection top

Bruker X8 APEXII area-detector diffractometer	2614 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2105 reflections with I > 2σ(I)
T_min = 0.544, T_max = 0.769	R_int = 0.036
19471 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.110	H-atom parameters constrained
S = 0.97	Δρ_max = 0.33 e Å⁻³
2614 reflections	Δρ_min = −0.44 e Å⁻³
199 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.47189 (2)	1.27997 (6)	0.426257 (19)	0.05859 (18)
O1	0.21672 (14)	0.1051 (4)	0.11117 (12)	0.0605 (6)
N1	0.28026 (15)	0.7379 (4)	0.34628 (14)	0.0407 (6)
N2	0.26035 (13)	0.4610 (4)	0.23929 (12)	0.0362 (5)
N3	0.37245 (14)	0.6006 (4)	0.20155 (13)	0.0415 (5)
C1	0.33253 (18)	0.9234 (5)	0.38466 (16)	0.0437 (6)
H1	0.3214	0.9916	0.4265	0.052*
C2	0.40263 (16)	1.0193 (5)	0.36533 (15)	0.0399 (6)
C3	0.42374 (17)	0.9297 (5)	0.30393 (15)	0.0400 (6)
H3	0.4701	0.9949	0.2904	0.048*
C4	0.37115 (19)	0.7370 (4)	0.26428 (18)	0.0364 (6)
C5	0.30126 (16)	0.6536 (5)	0.28810 (15)	0.0347 (6)
C6	0.18408 (17)	0.3215 (5)	0.24445 (16)	0.0398 (6)
H6A	0.1851	0.3335	0.2973	0.048*
H6B	0.1923	0.1509	0.2344	0.048*
C7	0.09249 (16)	0.4032 (4)	0.18891 (15)	0.0373 (6)
C8	0.0798 (2)	0.6091 (6)	0.1437 (2)	0.0660 (9)
H8	0.1294	0.7050	0.1467	0.079*
C9	−0.0063 (3)	0.6757 (7)	0.0935 (3)	0.0863 (13)
H9	−0.0139	0.8138	0.0623	0.104*
C10	−0.0799 (2)	0.5399 (7)	0.0897 (2)	0.0752 (10)
H10	−0.1375	0.5839	0.0556	0.090*
C11	−0.0687 (2)	0.3409 (8)	0.1356 (2)	0.0706 (10)
H11	−0.1190	0.2505	0.1340	0.085*
C12	0.0171 (2)	0.2703 (5)	0.1851 (2)	0.0549 (8)
H12	0.0239	0.1319	0.2160	0.066*
C13	0.30648 (16)	0.4385 (5)	0.18846 (15)	0.0369 (6)
C14	0.2871 (2)	0.2623 (4)	0.12615 (18)	0.0428 (7)
C15	0.3289 (2)	0.2287 (6)	0.0754 (2)	0.0587 (9)
H15	0.3787	0.3147	0.0737	0.070*
C16	0.2825 (2)	0.0376 (6)	0.02513 (19)	0.0651 (9)
H16	0.2956	−0.0266	−0.0163	0.078*
C17	0.2169 (3)	−0.0318 (6)	0.04850 (19)	0.0683 (9)
H17	0.1761	−0.1570	0.0257	0.082*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0540 (3)	0.0519 (2)	0.0593 (3)	−0.00676 (12)	0.00831 (18)	−0.01181 (13)
O1	0.0659 (14)	0.0602 (13)	0.0594 (14)	−0.0183 (11)	0.0276 (11)	−0.0162 (10)
N1	0.0330 (13)	0.0534 (13)	0.0395 (14)	0.0029 (9)	0.0176 (11)	−0.0003 (10)
N2	0.0268 (11)	0.0449 (11)	0.0378 (13)	−0.0025 (9)	0.0130 (9)	−0.0003 (9)
N3	0.0317 (12)	0.0538 (14)	0.0424 (13)	−0.0020 (10)	0.0175 (10)	−0.0037 (10)
C1	0.0380 (15)	0.0519 (15)	0.0416 (16)	0.0036 (12)	0.0150 (12)	−0.0047 (12)
C2	0.0330 (14)	0.0416 (13)	0.0391 (16)	0.0017 (11)	0.0061 (12)	−0.0006 (11)
C3	0.0296 (14)	0.0464 (14)	0.0440 (16)	−0.0006 (11)	0.0135 (12)	0.0030 (11)
C4	0.0281 (15)	0.0436 (14)	0.0396 (17)	0.0007 (10)	0.0147 (13)	0.0028 (11)
C5	0.0253 (13)	0.0419 (13)	0.0361 (15)	0.0025 (10)	0.0101 (11)	0.0027 (11)
C6	0.0345 (15)	0.0458 (14)	0.0414 (16)	−0.0046 (11)	0.0165 (13)	0.0047 (11)
C7	0.0288 (13)	0.0408 (13)	0.0437 (16)	−0.0052 (10)	0.0152 (12)	−0.0047 (11)
C8	0.0388 (17)	0.063 (2)	0.086 (2)	−0.0040 (14)	0.0108 (17)	0.0219 (17)
C9	0.062 (2)	0.069 (2)	0.102 (3)	0.0088 (19)	−0.001 (2)	0.025 (2)
C10	0.0368 (19)	0.089 (3)	0.083 (3)	0.0077 (17)	0.0013 (17)	−0.012 (2)
C11	0.0350 (19)	0.093 (3)	0.081 (3)	−0.0156 (17)	0.0181 (19)	−0.015 (2)
C12	0.0417 (19)	0.0643 (19)	0.061 (2)	−0.0119 (13)	0.0216 (16)	0.0033 (14)
C13	0.0291 (13)	0.0446 (13)	0.0366 (15)	0.0046 (10)	0.0116 (11)	0.0011 (11)
C14	0.0353 (16)	0.0481 (15)	0.0427 (18)	0.0018 (11)	0.0117 (13)	−0.0002 (11)
C15	0.053 (2)	0.074 (2)	0.054 (2)	−0.0036 (14)	0.0244 (18)	−0.0152 (15)
C16	0.076 (2)	0.070 (2)	0.049 (2)	0.0112 (18)	0.0221 (17)	−0.0105 (15)
C17	0.091 (3)	0.0550 (18)	0.054 (2)	−0.0113 (18)	0.0199 (19)	−0.0155 (15)

Geometric parameters (Å, º) top

Br1—C2	1.897 (3)	C7—C8	1.372 (4)
O1—C14	1.355 (3)	C7—C12	1.377 (4)
O1—C17	1.378 (4)	C8—C9	1.387 (5)
N1—C5	1.317 (3)	C8—H8	0.93
N1—C1	1.337 (3)	C9—C10	1.362 (5)
N2—C5	1.383 (3)	C9—H9	0.93
N2—C13	1.388 (3)	C10—C11	1.351 (5)
N2—C6	1.462 (3)	C10—H10	0.93
N3—C13	1.324 (3)	C11—C12	1.385 (5)
N3—C4	1.382 (4)	C11—H11	0.93
C1—C2	1.388 (4)	C12—H12	0.93
C1—H1	0.93	C13—C14	1.444 (4)
C2—C3	1.382 (4)	C14—C15	1.341 (5)
C3—C4	1.376 (4)	C15—C16	1.412 (4)
C3—H3	0.93	C15—H15	0.93
C4—C5	1.408 (4)	C16—C17	1.317 (5)
C6—C7	1.505 (4)	C16—H16	0.93
C6—H6A	0.97	C17—H17	0.93
C6—H6B	0.97

C14—O1—C17	105.2 (2)	C7—C8—C9	120.7 (3)
C5—N1—C1	113.9 (2)	C7—C8—H8	119.7
C5—N2—C13	105.62 (19)	C9—C8—H8	119.7
C5—N2—C6	123.9 (2)	C10—C9—C8	120.3 (4)
C13—N2—C6	130.5 (2)	C10—C9—H9	119.8
C13—N3—C4	105.2 (2)	C8—C9—H9	119.8
N1—C1—C2	123.4 (3)	C11—C10—C9	119.6 (3)
N1—C1—H1	118.3	C11—C10—H10	120.2
C2—C1—H1	118.3	C9—C10—H10	120.2
C3—C2—C1	122.2 (2)	C10—C11—C12	120.6 (3)
C3—C2—Br1	119.38 (19)	C10—C11—H11	119.7
C1—C2—Br1	118.46 (19)	C12—C11—H11	119.7
C4—C3—C2	115.2 (2)	C7—C12—C11	120.6 (3)
C4—C3—H3	122.4	C7—C12—H12	119.7
C2—C3—H3	122.4	C11—C12—H12	119.7
C3—C4—N3	131.8 (2)	N3—C13—N2	113.1 (2)
C3—C4—C5	118.4 (3)	N3—C13—C14	121.1 (2)
N3—C4—C5	109.9 (2)	N2—C13—C14	125.8 (2)
N1—C5—N2	126.8 (2)	C15—C14—O1	110.5 (3)
N1—C5—C4	127.0 (2)	C15—C14—C13	129.1 (3)
N2—C5—C4	106.2 (2)	O1—C14—C13	120.3 (3)
N2—C6—C7	114.5 (2)	C14—C15—C16	106.7 (3)
N2—C6—H6A	108.6	C14—C15—H15	126.6
C7—C6—H6A	108.6	C16—C15—H15	126.6
N2—C6—H6B	108.6	C17—C16—C15	106.4 (3)
C7—C6—H6B	108.6	C17—C16—H16	126.8
H6A—C6—H6B	107.6	C15—C16—H16	126.8
C8—C7—C12	118.1 (3)	C16—C17—O1	111.2 (3)
C8—C7—C6	123.2 (2)	C16—C17—H17	124.4
C12—C7—C6	118.6 (2)	O1—C17—H17	124.4

C5—N1—C1—C2	0.0 (4)	C6—C7—C8—C9	−180.0 (3)
N1—C1—C2—C3	0.2 (4)	C7—C8—C9—C10	1.4 (7)
N1—C1—C2—Br1	−179.2 (2)	C8—C9—C10—C11	0.7 (7)
C1—C2—C3—C4	−0.8 (4)	C9—C10—C11—C12	−1.7 (6)
Br1—C2—C3—C4	178.56 (19)	C8—C7—C12—C11	1.3 (5)
C2—C3—C4—N3	−179.3 (3)	C6—C7—C12—C11	179.1 (3)
C2—C3—C4—C5	1.2 (4)	C10—C11—C12—C7	0.7 (6)
C13—N3—C4—C3	179.7 (3)	C4—N3—C13—N2	0.5 (3)
C13—N3—C4—C5	−0.7 (3)	C4—N3—C13—C14	179.9 (2)
C1—N1—C5—N2	178.7 (2)	C5—N2—C13—N3	0.0 (3)
C1—N1—C5—C4	0.4 (4)	C6—N2—C13—N3	179.7 (2)
C13—N2—C5—N1	−179.0 (2)	C5—N2—C13—C14	−179.4 (2)
C6—N2—C5—N1	1.3 (4)	C6—N2—C13—C14	0.3 (4)
C13—N2—C5—C4	−0.4 (3)	C17—O1—C14—C15	0.7 (4)
C6—N2—C5—C4	179.9 (2)	C17—O1—C14—C13	179.1 (3)
C3—C4—C5—N1	−1.1 (4)	N3—C13—C14—C15	1.2 (5)
N3—C4—C5—N1	179.3 (2)	N2—C13—C14—C15	−179.5 (3)
C3—C4—C5—N2	−179.7 (2)	N3—C13—C14—O1	−176.9 (2)
N3—C4—C5—N2	0.7 (3)	N2—C13—C14—O1	2.4 (4)
C5—N2—C6—C7	96.8 (3)	O1—C14—C15—C16	−0.3 (4)
C13—N2—C6—C7	−82.8 (3)	C13—C14—C15—C16	−178.5 (3)
N2—C6—C7—C8	−7.5 (4)	C14—C15—C16—C17	−0.3 (4)
N2—C6—C7—C12	174.8 (2)	C15—C16—C17—O1	0.7 (4)
C12—C7—C8—C9	−2.3 (5)	C14—O1—C17—C16	−0.8 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N3ⁱ	0.93	2.51	3.399 (4)	160

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

Experimental details

Crystal data
Chemical formula	C₁₇H₁₂BrN₃O
M_r	354.21
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	15.8422 (3), 5.4747 (1), 18.4243 (3)
β (°)	111.509 (1)
V (Å³)	1486.68 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.77
Crystal size (mm)	0.25 × 0.25 × 0.10

Data collection
Diffractometer	Bruker X8 APEXII area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.544, 0.769
No. of measured, independent and observed [I > 2σ(I)] reflections	19471, 2614, 2105
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.110, 0.97
No. of reflections	2614
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.44

Computer programs: APEX2 (Bruker, 2008), SAINT (Bruker, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), X-SEED (Barbour, 2001), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···N3ⁱ	0.93	2.51	3.399 (4)	160

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

Acknowledgements

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

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
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