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

Abstract

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,

• a = 27.0174 (11) Å

• b = 6.0141 (2) Å

• c = 16.6121 (6) Å

• β = 110.343 (2)°

• V = 2530.87 (16) ų

• 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[F ² > 2σ(F ²)] = 0.038

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) .

supplementary crystallographic information

Experimental

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.

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.94-0.99 Å) and were included in the refinement in the riding model approximation, with U(H) set to 1.2U(C). The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.86±0.01 Å; its displacement parameter was refined isotropically.

Figures

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.

Crystal data

C11H11BrN4O3	F(000) = 1312
Mr = 327.15	Dx = 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

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

Refinement

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(Fo2) + (0.0269P)2 + 1.8498P] where P = (Fo2 + 2Fc2)/3
2224 reflections	(Δ/σ)max = 0.001
176 parameters	Δρmax = 0.36 e Å−3
1 restraint	Δρmin = −0.36 e Å−3

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

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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 codes: (i) −x+1/2, −y+1/2, −z+1.