2-(2-Methyl-5-nitro-1H-imidazol-1-yl)ethyl 3-bromo­benzoate

Bahadur, S.; Anis, I.; Shah, M.R.; Singh, K.

doi:10.1107/S1600536809015499

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Page o1176

doi:10.1107/S1600536809015499

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2-(2-Methyl-5-nitro-1H-imidazol-1-yl)ethyl 3-bromobenzoate

Sher Bahadur,^a Itrat Anis,^b Muhammad Raza Shah ^a ^* and Kuldip Singh ^c

^aHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, ^bDepartment of Chemistry, University of Karachi, Karachi 75270, Pakistan, and ^cDepartment of Chemistry, University of Leicester, George Porter Building, University Road, Leicester LE1 7RH, England
^*Correspondence e-mail: raza_shahm@yahoo.com

(Received 16 April 2009; accepted 25 April 2009; online 30 April 2009)

The molecule of the title compound, C₁₃H₁₂BrN₃O₄, is non-planar, as indicated in the dihedral angle of 59.5 (4)° formed between the least-squares planes through the imidazole and benzene rings. In the crystal, molecules are connected via C—H⋯O contacts, forming a supramolecular chain.

Related literature

For potential pharmacological uses of benzoic acid derivatives, see: Correa-Basurto et al. (2005 ); Jetten et al. (1987 ); Kelly et al. (2007 ); Sato et al. (2005 ). For a related structure, see: Wang et al. (2008 ).

Experimental

Crystal data

C₁₃H₁₂BrN₃O₄
M_r = 354.17
Monoclinic, C c
a = 11.871 (2) Å
b = 19.840 (4) Å
c = 7.1983 (13) Å
β = 124.488 (3)°
V = 1397.4 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.96 mm⁻¹
T = 150 K
0.20 × 0.07 × 0.03 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.589, T_max = 0.916
5456 measured reflections
2680 independent reflections
1636 reflections with I > 2σ(I)
R_int = 0.087

Refinement

R[F² > 2σ(F²)] = 0.061
wR(F²) = 0.119
S = 0.86
2680 reflections
191 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.66 e Å⁻³
Δρ_min = −0.55 e Å⁻³
Absolute structure: Flack (1983 ), 1301 Friedel pairs
Flack parameter: 0.091 (17)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4a⋯O2ⁱ	0.99	2.59	3.494 (10)	152
Symmetry code: (i) x, y, z-1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 1999 ); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809015499/tk2425sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809015499/tk2425Isup2.hkl

checkCIF report

Comment top

Derivatives of benzoic acid offer promise as compounds that possess multifunctional physiological activity (hypolesterolemic, antitumor, antithrombic, etc.) and do not cause hypervitaminosis and other side-effects (Jetten et al. 1987). It has been reported that synthesized benzoic acid derivatives of the amide- and chalcone-series show inhibitory activity of squamous cell differentiation of rabbit traeheal epithelial cell but induce differentiation of mouse embryonal carcinoma F9 and human promyelocytic leukemia HL60 cells (Correa-Basurto et al., 2005). p-Aminobenzoic acid derivatives were evaluated as acetylcholinesterase inhibitors (AChEIs) (Sato et al., 2005). Benzoic acid derivatives have also been found to exhibit cytotoxic effects on the MDA-MB-435-S—F breast cancer cell line (Kelly et al., 2007).

In the crystal structure of the title compound (I), Fig. 1, the key C=O and C—N bond distances are in agreement with those observed in the related structure of imidazolmethyl phthalimide (Wang et al., 2008).

Related literature top

For potential pharmacological uses of benzoic acid derivatives, see: Correa-Basurto et al. (2005); Jetten et al. (1987); Kelly et al. (2007); Sato et al. (2005). For a related structure, see: Wang et al. (2008).

Experimental top

Metronidazole (5 g, 29.23 mmol) was added to 3-bromobenzoic acid (7.64 g, 38.01 mmol) dissolved in anhydrous CH₂Cl₂ (10 ml). Then 4-dimethylaminopyridine (0.15 equiv.) and dicyclohexylcarbodiimide (1.25 equiv) were added, and the resulting solution stirred. After 12 h, the solvent was evaporated under reduced pressure. The crude reaction mixture was subjected to flash column chromatography over silica gel, successively eluting with n-hexane–ethyl acetate (3:7) which afforded (I) in 70% yield. Colorless crystals were obtained from the slow evaporation of a CH₂Cl₂ solution of (I).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Molecular Structure of (I) show atom labelling and 30% displacement ellipsoids.

2-(2-Methyl-5-nitro-1H-imidazol-1-yl)ethyl 3-bromobenzoate top

Crystal data top

C₁₃H₁₂BrN₃O₄	F(000) = 712
M_r = 354.17	D_x = 1.683 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 616 reflections
a = 11.871 (2) Å	θ = 3.7–23.3°
b = 19.840 (4) Å	µ = 2.96 mm⁻¹
c = 7.1983 (13) Å	T = 150 K
β = 124.488 (3)°	Needle, colourless
V = 1397.4 (4) Å³	0.20 × 0.07 × 0.03 mm
Z = 4

Data collection top

Bruker APEX 2000 CCD area-detector diffractometer	2680 independent reflections
Radiation source: fine-focus sealed tube	1636 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.087
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→14
T_min = 0.589, T_max = 0.916	k = −24→23
5456 measured reflections	l = −8→8

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.119	w = 1/[σ²(F_o²) + (0.0345P)²] where P = (F_o² + 2F_c²)/3
S = 0.86	(Δ/σ)_max = 0.001
2680 reflections	Δρ_max = 0.66 e Å⁻³
191 parameters	Δρ_min = −0.55 e Å⁻³
2 restraints	Absolute structure: Flack (1983), 1301 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.091 (17)

Crystal data top

C₁₃H₁₂BrN₃O₄	V = 1397.4 (4) Å³
M_r = 354.17	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 11.871 (2) Å	µ = 2.96 mm⁻¹
b = 19.840 (4) Å	T = 150 K
c = 7.1983 (13) Å	0.20 × 0.07 × 0.03 mm
β = 124.488 (3)°

Data collection top

Bruker APEX 2000 CCD area-detector diffractometer	2680 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1636 reflections with I > 2σ(I)
T_min = 0.589, T_max = 0.916	R_int = 0.087
5456 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.061	H-atom parameters constrained
wR(F²) = 0.119	Δρ_max = 0.66 e Å⁻³
S = 0.86	Δρ_min = −0.55 e Å⁻³
2680 reflections	Absolute structure: Flack (1983), 1301 Friedel pairs
191 parameters	Absolute structure parameter: 0.091 (17)
2 restraints

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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.

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

	x	y	z	U_iso*/U_eq
Br1	0.81001 (10)	0.59782 (5)	0.72927 (13)	0.0588 (3)
O1	0.0138 (5)	0.6343 (3)	0.5323 (9)	0.0363 (14)
O2	0.0896 (5)	0.7074 (3)	0.8019 (9)	0.0434 (15)
O3	0.2933 (5)	0.5475 (3)	0.4184 (9)	0.0309 (14)
O4	0.2623 (6)	0.4375 (3)	0.4381 (11)	0.0437 (16)
N1	0.0966 (6)	0.6786 (3)	0.6597 (11)	0.0322 (16)
N2	0.2152 (6)	0.6769 (3)	0.4669 (9)	0.0234 (14)
N3	0.3904 (6)	0.7449 (3)	0.6962 (11)	0.0324 (16)
C1	0.2023 (8)	0.6976 (4)	0.6362 (12)	0.0261 (17)
C2	0.3074 (10)	0.7391 (4)	0.7650 (18)	0.042 (3)
H2	0.3216	0.7622	0.8924	0.050*
C3	0.3307 (8)	0.7090 (4)	0.5099 (13)	0.0281 (18)
C4	0.1261 (7)	0.6329 (4)	0.2730 (12)	0.0280 (18)
H4A	0.1413	0.6422	0.1537	0.034*
H4B	0.0295	0.6436	0.2115	0.034*
C5	0.1513 (7)	0.5597 (4)	0.3332 (13)	0.0294 (19)
H5A	0.1344	0.5490	0.4498	0.035*
H5B	0.0903	0.5315	0.1988	0.035*
C6	0.3328 (8)	0.4832 (4)	0.4592 (12)	0.0222 (18)
C7	0.4765 (8)	0.4759 (4)	0.5349 (12)	0.0263 (19)
C8	0.5272 (9)	0.4134 (4)	0.5409 (13)	0.041 (2)
H8	0.4686	0.3754	0.4966	0.049*
C9	0.6614 (10)	0.4036 (5)	0.6098 (14)	0.048 (2)
H9	0.6962	0.3596	0.6198	0.057*
C10	0.7422 (9)	0.4597 (5)	0.6630 (13)	0.049 (3)
H10	0.8333	0.4538	0.7053	0.059*
C11	0.6978 (8)	0.5231 (4)	0.6579 (12)	0.035 (2)
C12	0.5625 (7)	0.5325 (4)	0.5850 (12)	0.032 (2)
H12	0.5277	0.5768	0.5688	0.038*
C13	0.3796 (8)	0.7029 (4)	0.3597 (13)	0.043 (2)
H13A	0.3319	0.7359	0.2373	0.064*
H13B	0.3608	0.6573	0.2962	0.064*
H13C	0.4781	0.7115	0.4472	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.0321 (4)	0.0955 (8)	0.0384 (5)	−0.0218 (7)	0.0137 (4)	0.0017 (7)
O1	0.025 (3)	0.046 (4)	0.035 (3)	−0.002 (3)	0.014 (3)	0.006 (3)
O2	0.038 (3)	0.065 (4)	0.039 (3)	0.001 (3)	0.028 (3)	−0.007 (3)
O3	0.025 (3)	0.031 (3)	0.036 (4)	0.002 (3)	0.017 (3)	0.005 (3)
O4	0.042 (4)	0.031 (3)	0.062 (4)	−0.003 (3)	0.032 (4)	0.005 (3)
N1	0.021 (4)	0.044 (4)	0.030 (4)	0.007 (3)	0.014 (3)	0.013 (3)
N2	0.025 (4)	0.028 (4)	0.018 (3)	−0.009 (3)	0.012 (3)	−0.003 (3)
N3	0.031 (4)	0.036 (4)	0.036 (4)	−0.007 (3)	0.022 (4)	−0.012 (3)
C1	0.024 (4)	0.031 (4)	0.025 (4)	−0.005 (4)	0.015 (4)	−0.006 (4)
C2	0.030 (5)	0.030 (5)	0.059 (7)	0.003 (5)	0.021 (5)	0.000 (5)
C3	0.035 (5)	0.024 (4)	0.030 (5)	0.006 (4)	0.021 (4)	0.008 (4)
C4	0.027 (4)	0.039 (5)	0.022 (4)	−0.005 (4)	0.017 (4)	0.000 (4)
C5	0.021 (4)	0.043 (5)	0.028 (5)	−0.003 (4)	0.017 (4)	0.008 (4)
C6	0.027 (5)	0.028 (5)	0.010 (4)	−0.004 (4)	0.010 (3)	−0.002 (4)
C7	0.024 (4)	0.037 (5)	0.019 (4)	0.005 (4)	0.013 (4)	−0.002 (4)
C8	0.044 (6)	0.046 (6)	0.024 (5)	0.004 (5)	0.014 (4)	0.003 (4)
C9	0.049 (6)	0.049 (6)	0.041 (6)	0.022 (5)	0.023 (5)	0.011 (5)
C10	0.038 (5)	0.085 (8)	0.035 (6)	0.012 (5)	0.027 (5)	0.012 (5)
C11	0.029 (5)	0.050 (6)	0.021 (4)	0.005 (4)	0.011 (4)	0.000 (4)
C12	0.025 (4)	0.045 (5)	0.021 (4)	0.009 (4)	0.010 (4)	0.009 (4)
C13	0.053 (6)	0.043 (5)	0.044 (5)	−0.010 (5)	0.035 (5)	0.006 (4)

Geometric parameters (Å, º) top

Br1—C11	1.861 (8)	C4—H4B	0.9900
O1—N1	1.248 (7)	C5—H5A	0.9900
O2—N1	1.216 (8)	C5—H5B	0.9900
O3—C6	1.334 (9)	C6—C7	1.475 (10)
O3—C5	1.451 (8)	C7—C8	1.369 (10)
O4—C6	1.183 (9)	C7—C12	1.420 (11)
N1—C1	1.410 (9)	C8—C9	1.389 (12)
N2—C1	1.374 (9)	C8—H8	0.9500
N2—C3	1.378 (9)	C9—C10	1.375 (11)
N2—C4	1.468 (8)	C9—H9	0.9500
N3—C3	1.317 (9)	C10—C11	1.356 (11)
N3—C2	1.334 (11)	C10—H10	0.9500
C1—C2	1.336 (12)	C11—C12	1.391 (10)
C2—H2	0.9500	C12—H12	0.9500
C3—C13	1.493 (10)	C13—H13A	0.9800
C4—C5	1.497 (10)	C13—H13B	0.9800
C4—H4A	0.9900	C13—H13C	0.9800

C6—O3—C5	115.6 (6)	H5A—C5—H5B	108.7
O2—N1—O1	123.3 (6)	O4—C6—O3	124.8 (7)
O2—N1—C1	117.7 (7)	O4—C6—C7	124.0 (8)
O1—N1—C1	119.0 (6)	O3—C6—C7	111.3 (7)
C1—N2—C3	105.0 (6)	C8—C7—C12	118.0 (7)
C1—N2—C4	129.7 (6)	C8—C7—C6	119.7 (8)
C3—N2—C4	125.2 (6)	C12—C7—C6	122.1 (7)
C3—N3—C2	104.3 (7)	C7—C8—C9	122.2 (8)
C2—C1—N2	105.7 (7)	C7—C8—H8	118.9
C2—C1—N1	128.8 (8)	C9—C8—H8	118.9
N2—C1—N1	125.4 (6)	C10—C9—C8	117.7 (8)
N3—C2—C1	113.0 (9)	C10—C9—H9	121.1
N3—C2—H2	123.5	C8—C9—H9	121.1
C1—C2—H2	123.5	C11—C10—C9	122.9 (8)
N3—C3—N2	111.8 (6)	C11—C10—H10	118.5
N3—C3—C13	125.1 (7)	C9—C10—H10	118.5
N2—C3—C13	123.0 (7)	C10—C11—C12	118.9 (8)
N2—C4—C5	112.5 (6)	C10—C11—Br1	121.6 (7)
N2—C4—H4A	109.1	C12—C11—Br1	119.3 (6)
C5—C4—H4A	109.1	C11—C12—C7	120.0 (8)
N2—C4—H4B	109.1	C11—C12—H12	120.0
C5—C4—H4B	109.1	C7—C12—H12	120.0
H4A—C4—H4B	107.8	C3—C13—H13A	109.5
O3—C5—C4	106.1 (6)	C3—C13—H13B	109.5
O3—C5—H5A	110.5	H13A—C13—H13B	109.5
C4—C5—H5A	110.5	C3—C13—H13C	109.5
O3—C5—H5B	110.5	H13A—C13—H13C	109.5
C4—C5—H5B	110.5	H13B—C13—H13C	109.5

C3—N2—C1—C2	−0.1 (8)	C6—O3—C5—C4	−173.1 (6)
C4—N2—C1—C2	−177.6 (7)	N2—C4—C5—O3	−59.7 (7)
C3—N2—C1—N1	178.8 (7)	C5—O3—C6—O4	−2.7 (11)
C4—N2—C1—N1	1.3 (12)	C5—O3—C6—C7	177.4 (6)
O2—N1—C1—C2	7.5 (12)	O4—C6—C7—C8	13.3 (12)
O1—N1—C1—C2	−173.8 (8)	O3—C6—C7—C8	−166.7 (7)
O2—N1—C1—N2	−171.2 (7)	O4—C6—C7—C12	−172.0 (7)
O1—N1—C1—N2	7.5 (10)	O3—C6—C7—C12	8.0 (10)
C3—N3—C2—C1	3.8 (10)	C12—C7—C8—C9	4.8 (12)
N2—C1—C2—N3	−2.3 (10)	C6—C7—C8—C9	179.8 (7)
N1—C1—C2—N3	178.8 (7)	C7—C8—C9—C10	−3.0 (13)
C2—N3—C3—N2	−3.8 (9)	C8—C9—C10—C11	2.2 (13)
C2—N3—C3—C13	176.0 (8)	C9—C10—C11—C12	−3.3 (13)
C1—N2—C3—N3	2.5 (8)	C9—C10—C11—Br1	−179.6 (6)
C4—N2—C3—N3	−179.8 (6)	C10—C11—C12—C7	5.1 (11)
C1—N2—C3—C13	−177.3 (7)	Br1—C11—C12—C7	−178.5 (6)
C4—N2—C3—C13	0.3 (11)	C8—C7—C12—C11	−5.8 (11)
C1—N2—C4—C5	−81.4 (9)	C6—C7—C12—C11	179.4 (7)
C3—N2—C4—C5	101.6 (8)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4a···O2ⁱ	0.99	2.59	3.494 (10)	152

Symmetry code: (i) x, y, z−1.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂BrN₃O₄
M_r	354.17
Crystal system, space group	Monoclinic, Cc
Temperature (K)	150
a, b, c (Å)	11.871 (2), 19.840 (4), 7.1983 (13)
β (°)	124.488 (3)
V (Å³)	1397.4 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.96
Crystal size (mm)	0.20 × 0.07 × 0.03

Data collection
Diffractometer	Bruker APEX 2000 CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.589, 0.916
No. of measured, independent and observed [I > 2σ(I)] reflections	5456, 2680, 1636
R_int	0.087
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.061, 0.119, 0.86
No. of reflections	2680
No. of parameters	191
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.66, −0.55
Absolute structure	Flack (1983), 1301 Friedel pairs
Absolute structure parameter	0.091 (17)

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4a···O2ⁱ	0.99	2.59	3.494 (10)	152

Symmetry code: (i) x, y, z−1.

Acknowledgements

The authors thank the Pakistan Science Foundation for financial support.

References

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