6-Bromo-1-[2-(2-oxo-1,3-oxazolidin-3-yl)eth­yl]-1H-imidazo[4,5-b]pyridin-2(3H)-one

Bel-Ghacham, H.; Kandri Rodi, Y.; Saffon, N.; Essassi, E.M.; Ng, S.W.

doi:10.1107/S1600536810002679

organic compounds

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6-Bromo-1-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-1H-imidazo[4,5-b]pyridin-2(3H)-one

H. Bel-Ghacham,^a Y. Kandri Rodi,^a Natalie Saffon,^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, Fés, Morocco, ^bService Commun Rayons-X FR2599, Université Paul Sabatier Bâtiment 2R1, 118 route de Narbonne, Toulouse, France, ^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 20 January 2010; accepted 21 January 2010; online 27 January 2010)

The title compound, C₁₁H₁₁BrN₄O₃, features an ethane fragment substituted with an almost planar (r.m.s. deviation = 0.019 Å) imidazo[4,5-b]pyridone ring system and an envelope-shaped oxazolidine unit on separate C atoms. The N—CH₂—CH₂—N torsion angle is 52.5 (4)°. In the crystal, pairs of molecules are linked by N—H⋯O hydrogen bonds into centrosymmetric dimers.

Related literature

For the medicinal properties of imidazo[4,5-b]pyridines, see: Barraclough et al. (1990 ); Bianchi et al. (1983 ); Clark et al. (1978 ); Janssens et al. (1985 ); Temple et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₁BrN₄O₃
M_r = 327.15
Monoclinic, C 2/c
a = 27.0174 (11) Å
b = 6.0141 (2) Å
c = 16.6121 (6) Å
β = 110.343 (2)°
V = 2530.87 (16) Å³
Z = 8
Mo Kα radiation
μ = 3.26 mm⁻¹
T = 173 K
0.40 × 0.20 × 0.05 mm

Data collection

Bruker APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.356, T_max = 0.854
9174 measured reflections
2224 independent reflections
1633 reflections with I > 2σ(I)
R_int = 0.062
Standard reflections: 0

Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.077
S = 1.02
2224 reflections
176 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯O3ⁱ	0.86 (1)	1.94 (1)	2.781 (4)	167 (3)
Symmetry code: (i) $[-x+{\script{1\over 2}}, -y+{\script{1\over 2}}, -z+1]$ .

Data collection: APEX2 (Bruker, 2005 ); cell refinement: SAINT (Bruker, 2005); 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: https://doi.org/10.1107/S1600536810002679/bt5180sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810002679/bt5180Isup2.hkl

checkCIF report

Related literature top

For the medicinal properties of imidazo[4,5-b]pyridines, see: Barraclough et al. (1990); Bianchi et al. (1983); Clark et al. (1978); Janssens et al. (1985); Temple et al. (1987).

Experimental top

To 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 (30 ml) was added bis(2-chloroethyl)amine hydrochloride (2.5 mmol). The mixture was heated for 48 h. After the completion of the reaction (as monitored by TLC), the inorganic material salt was filtered and the solvent was removed under reduced pressure. The residue was purified by column chromatography on silica gel by using (ethylacetate/hexane: 2/1) as eluent to furnish colorless crystals.

Structure description top

For the medicinal properties of imidazo[4,5-b]pyridines, see: Barraclough et al. (1990); Bianchi et al. (1983); Clark et al. (1978); Janssens et al. (1985); Temple et al. (1987).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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. Anisotropic displacement ellipsoid plot (Barbour, 2001) of C₁₁H₁₁BrN₄O₃ at the 70% probability level; hydrogen atoms are drawn as spheres of an arbitrary radius.

6-Bromo-1-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-1H- imidazo[4,5-b]pyridin-2(3H)-one top

Crystal data top

C₁₁H₁₁BrN₄O₃	F(000) = 1312
M_r = 327.15	D_x = 1.717 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1559 reflections
a = 27.0174 (11) Å	θ = 2.6–22.4°
b = 6.0141 (2) Å	µ = 3.26 mm⁻¹
c = 16.6121 (6) Å	T = 173 K
β = 110.343 (2)°	Plate, colorless
V = 2530.87 (16) Å³	0.40 × 0.20 × 0.05 mm
Z = 8

Data collection top

Bruker APEXII diffractometer	2224 independent reflections
Radiation source: fine-focus sealed tube	1633 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
φ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −26→32
T_min = 0.356, T_max = 0.854	k = −7→7
9174 measured reflections	l = −19→19

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0269P)² + 1.8498P] where P = (F_o² + 2F_c²)/3
2224 reflections	(Δ/σ)_max = 0.001
176 parameters	Δρ_max = 0.36 e Å⁻³
1 restraint	Δρ_min = −0.36 e Å⁻³

Crystal data top

C₁₁H₁₁BrN₄O₃	V = 2530.87 (16) Å³
M_r = 327.15	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 27.0174 (11) Å	µ = 3.26 mm⁻¹
b = 6.0141 (2) Å	T = 173 K
c = 16.6121 (6) Å	0.40 × 0.20 × 0.05 mm
β = 110.343 (2)°

Data collection top

Bruker APEXII diffractometer	2224 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1633 reflections with I > 2σ(I)
T_min = 0.356, T_max = 0.854	R_int = 0.062
9174 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	1 restraint
wR(F²) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.36 e Å⁻³
2224 reflections	Δρ_min = −0.36 e Å⁻³
176 parameters

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

	x	y	z	U_iso*/U_eq
Br1	0.030317 (17)	1.14052 (7)	0.39869 (3)	0.03436 (15)
O1	0.07133 (11)	0.4365 (4)	0.17338 (18)	0.0398 (8)
O2	0.14847 (12)	0.2803 (5)	0.25167 (18)	0.0447 (8)
O3	0.26482 (10)	0.4281 (4)	0.42343 (15)	0.0266 (6)
N1	0.14287 (12)	0.6468 (5)	0.21101 (17)	0.0236 (7)
N2	0.20224 (12)	0.7116 (5)	0.38942 (18)	0.0197 (7)
N3	0.19871 (12)	0.4599 (5)	0.48386 (18)	0.0225 (7)
H3	0.2052 (13)	0.339 (3)	0.5132 (18)	0.022 (10)*
N4	0.12421 (12)	0.6066 (5)	0.51587 (18)	0.0242 (7)
C1	0.12398 (18)	0.4418 (7)	0.2151 (2)	0.0307 (10)
C2	0.05337 (18)	0.6589 (7)	0.1444 (3)	0.0565 (14)
H2A	0.0354	0.7266	0.1812	0.068*
H2B	0.0286	0.6568	0.0843	0.068*
C3	0.10292 (17)	0.7865 (6)	0.1514 (3)	0.0366 (11)
H3A	0.1079	0.7975	0.0953	0.044*
H3B	0.1026	0.9376	0.1749	0.044*
C4	0.19838 (15)	0.6905 (6)	0.2399 (2)	0.0261 (9)
H4A	0.2065	0.7762	0.1951	0.031*
H4B	0.2176	0.5474	0.2474	0.031*
C5	0.21827 (15)	0.8193 (6)	0.3239 (2)	0.0221 (9)
H5A	0.2573	0.8290	0.3439	0.027*
H5B	0.2040	0.9725	0.3143	0.027*
C6	0.22613 (15)	0.5212 (6)	0.4313 (2)	0.0220 (9)
C7	0.15790 (14)	0.6070 (6)	0.4745 (2)	0.0198 (8)
C8	0.08786 (15)	0.7701 (6)	0.4925 (2)	0.0268 (9)
H8	0.0624	0.7777	0.5201	0.032*
C9	0.08554 (15)	0.9282 (6)	0.4302 (2)	0.0227 (9)
C10	0.12232 (15)	0.9304 (6)	0.3887 (2)	0.0220 (9)
H10	0.1218	1.0386	0.3468	0.026*
C11	0.15928 (14)	0.7649 (6)	0.4130 (2)	0.0183 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0348 (3)	0.0294 (3)	0.0412 (2)	0.0106 (2)	0.01603 (19)	0.0026 (2)
O1	0.0332 (19)	0.0294 (17)	0.0488 (19)	−0.0102 (14)	0.0042 (15)	−0.0006 (14)
O2	0.055 (2)	0.0231 (17)	0.0475 (19)	0.0033 (15)	0.0068 (16)	0.0151 (14)
O3	0.0277 (17)	0.0288 (16)	0.0264 (14)	0.0084 (13)	0.0134 (13)	0.0087 (11)
N1	0.029 (2)	0.0179 (18)	0.0216 (16)	−0.0027 (16)	0.0057 (14)	0.0021 (14)
N2	0.0232 (18)	0.0189 (17)	0.0178 (15)	−0.0005 (14)	0.0081 (14)	0.0051 (13)
N3	0.030 (2)	0.0186 (19)	0.0194 (17)	0.0056 (15)	0.0091 (15)	0.0093 (14)
N4	0.0270 (19)	0.0258 (19)	0.0222 (16)	0.0046 (15)	0.0116 (15)	0.0050 (14)
C1	0.042 (3)	0.024 (2)	0.026 (2)	−0.005 (2)	0.010 (2)	−0.0023 (18)
C2	0.043 (3)	0.035 (3)	0.072 (3)	0.003 (3)	−0.005 (3)	0.003 (3)
C3	0.047 (3)	0.021 (2)	0.033 (2)	0.006 (2)	0.003 (2)	0.0018 (18)
C4	0.031 (2)	0.029 (2)	0.025 (2)	−0.0018 (18)	0.0185 (19)	0.0000 (17)
C5	0.023 (2)	0.023 (2)	0.0200 (19)	−0.0004 (17)	0.0075 (16)	0.0040 (16)
C6	0.025 (2)	0.022 (2)	0.0183 (19)	−0.0003 (18)	0.0070 (18)	0.0022 (16)
C7	0.021 (2)	0.018 (2)	0.0183 (18)	0.0015 (17)	0.0048 (16)	0.0007 (16)
C8	0.026 (2)	0.031 (2)	0.027 (2)	−0.0008 (19)	0.0140 (19)	−0.0025 (18)
C9	0.024 (2)	0.019 (2)	0.025 (2)	0.0039 (16)	0.0088 (18)	−0.0012 (16)
C10	0.029 (2)	0.018 (2)	0.0182 (19)	0.0031 (17)	0.0066 (17)	0.0022 (15)
C11	0.022 (2)	0.019 (2)	0.0143 (18)	−0.0030 (17)	0.0064 (17)	−0.0032 (16)

Geometric parameters (Å, º) top

Br1—C9	1.894 (4)	C2—C3	1.512 (6)
O1—C1	1.349 (5)	C2—H2A	0.9900
O1—C2	1.447 (5)	C2—H2B	0.9900
O2—C1	1.213 (4)	C3—H3A	0.9900
O3—C6	1.232 (4)	C3—H3B	0.9900
N1—C1	1.345 (5)	C4—C5	1.521 (5)
N1—C4	1.431 (4)	C4—H4A	0.9900
N1—C3	1.452 (5)	C4—H4B	0.9900
N2—C6	1.378 (4)	C5—H5A	0.9900
N2—C11	1.385 (4)	C5—H5B	0.9900
N2—C5	1.457 (4)	C7—C11	1.405 (5)
N3—C6	1.377 (4)	C8—C9	1.390 (5)
N3—C7	1.380 (4)	C8—H8	0.9500
N3—H3	0.859 (10)	C9—C10	1.393 (5)
N4—C7	1.318 (4)	C10—C11	1.368 (5)
N4—C8	1.348 (4)	C10—H10	0.9500

C1—O1—C2	108.7 (3)	C5—C4—H4A	108.9
C1—N1—C4	121.6 (3)	N1—C4—H4B	108.9
C1—N1—C3	111.1 (3)	C5—C4—H4B	108.9
C4—N1—C3	124.5 (3)	H4A—C4—H4B	107.7
C6—N2—C11	109.9 (3)	N2—C5—C4	110.9 (3)
C6—N2—C5	122.6 (3)	N2—C5—H5A	109.5
C11—N2—C5	127.2 (3)	C4—C5—H5A	109.5
C6—N3—C7	110.0 (3)	N2—C5—H5B	109.5
C6—N3—H3	123 (2)	C4—C5—H5B	109.5
C7—N3—H3	127 (2)	H5A—C5—H5B	108.0
C7—N4—C8	114.5 (3)	O3—C6—N3	127.5 (3)
O2—C1—N1	127.5 (4)	O3—C6—N2	126.1 (3)
O2—C1—O1	122.2 (4)	N3—C6—N2	106.4 (3)
N1—C1—O1	110.3 (3)	N4—C7—N3	127.6 (3)
O1—C2—C3	104.9 (3)	N4—C7—C11	125.3 (3)
O1—C2—H2A	110.8	N3—C7—C11	107.1 (3)
C3—C2—H2A	110.8	N4—C8—C9	123.6 (3)
O1—C2—H2B	110.8	N4—C8—H8	118.2
C3—C2—H2B	110.8	C9—C8—H8	118.2
H2A—C2—H2B	108.8	C8—C9—C10	121.3 (3)
N1—C3—C2	100.8 (3)	C8—C9—Br1	119.6 (3)
N1—C3—H3A	111.6	C10—C9—Br1	119.1 (3)
C2—C3—H3A	111.6	C11—C10—C9	114.9 (3)
N1—C3—H3B	111.6	C11—C10—H10	122.6
C2—C3—H3B	111.6	C9—C10—H10	122.6
H3A—C3—H3B	109.4	C10—C11—N2	133.1 (3)
N1—C4—C5	113.3 (3)	C10—C11—C7	120.3 (3)
N1—C4—H4A	108.9	N2—C11—C7	106.6 (3)

C4—N1—C1—O2	10.3 (6)	C5—N2—C6—N3	−176.1 (3)
C3—N1—C1—O2	171.9 (4)	C8—N4—C7—N3	−179.2 (3)
C4—N1—C1—O1	−171.3 (3)	C8—N4—C7—C11	2.5 (5)
C3—N1—C1—O1	−9.7 (4)	C6—N3—C7—N4	−177.8 (3)
C2—O1—C1—O2	174.3 (4)	C6—N3—C7—C11	0.8 (4)
C2—O1—C1—N1	−4.2 (4)	C7—N4—C8—C9	−0.2 (5)
C1—O1—C2—C3	15.5 (5)	N4—C8—C9—C10	−1.6 (6)
C1—N1—C3—C2	18.3 (4)	N4—C8—C9—Br1	176.7 (3)
C4—N1—C3—C2	179.3 (3)	C8—C9—C10—C11	1.2 (5)
O1—C2—C3—N1	−19.6 (4)	Br1—C9—C10—C11	−177.2 (3)
C1—N1—C4—C5	−107.3 (4)	C9—C10—C11—N2	−178.5 (4)
C3—N1—C4—C5	93.6 (4)	C9—C10—C11—C7	0.9 (5)
C6—N2—C5—C4	75.4 (4)	C6—N2—C11—C10	−178.0 (4)
C11—N2—C5—C4	−97.5 (4)	C5—N2—C11—C10	−4.3 (6)
N1—C4—C5—N2	52.5 (4)	C6—N2—C11—C7	2.6 (4)
C7—N3—C6—O3	179.9 (4)	C5—N2—C11—C7	176.2 (3)
C7—N3—C6—N2	0.8 (4)	N4—C7—C11—C10	−2.9 (6)
C11—N2—C6—O3	178.8 (4)	N3—C7—C11—C10	178.5 (3)
C5—N2—C6—O3	4.8 (6)	N4—C7—C11—N2	176.6 (3)
C11—N2—C6—N3	−2.1 (4)	N3—C7—C11—N2	−2.0 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···O3ⁱ	0.86 (1)	1.94 (1)	2.781 (4)	167 (3)

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

Experimental details

Crystal data
Chemical formula	C₁₁H₁₁BrN₄O₃
M_r	327.15
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	173
a, b, c (Å)	27.0174 (11), 6.0141 (2), 16.6121 (6)
β (°)	110.343 (2)
V (Å³)	2530.87 (16)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.26
Crystal size (mm)	0.40 × 0.20 × 0.05

Data collection
Diffractometer	Bruker APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.356, 0.854
No. of measured, independent and observed [I > 2σ(I)] reflections	9174, 2224, 1633
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.077, 1.02
No. of reflections	2224
No. of parameters	176
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.36

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), 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
N3—H3···O3ⁱ	0.86 (1)	1.94 (1)	2.781 (4)	167 (3)

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

Acknowledgements

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

References

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

6-Bromo-1-[2-(2-oxo-1,3-oxazolidin-3-yl)eth­yl]-1H-imidazo[4,5-b]pyridin-2(3H)-one

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

6-Bromo-1-[2-(2-oxo-1,3-oxazolidin-3-yl)ethyl]-1H-imidazo[4,5-b]pyridin-2(3H)-one