Ethyl 4-[3-(1H-imidazol-1-yl)propyl­amino]-3-nitro­benzoate

Yeong Keng Yoon; Mohamed Ashraf Ali; Tan Soo Choon; Wan-Sin Loh; Hoong-Kun Fun

doi:10.1107/S1600536811036300

. 2011 Sep 14;67(Pt 10):o2606. doi: 10.1107/S1600536811036300

Ethyl 4-[3-(1H-imidazol-1-yl)propylamino]-3-nitrobenzoate

Yeong Keng Yoon ^a, Mohamed Ashraf Ali ^a, Tan Soo Choon ^a, Wan-Sin Loh ^b,^‡, Hoong-Kun Fun ^b,^*,^§

PMCID: PMC3201243 PMID: 22058754

Abstract

In the title compound, C₁₅H₁₈N₄O₄, the 1H-imidazole ring forms a dihedral angle of 67.12 (8)° with the benzene ring. An S(6) ring motif is formed via an intramolecular N—H⋯O hydrogen bond. In the crystal, neighbouring molecules are linked by a pair of intermolecular N—H⋯N hydrogen bonds, forming an inversion dimer. The dimers are further linked by a pair of C—H⋯O hydrogen bonds, leading to the formation of chain along [021]. A C—H⋯π interaction involving the centroid of the benzene ring is also observed between the chains.

Related literature

For applications of phenylenediamines, see: Sabelle (2006 ▶); Glebowska et al. (2009 ▶); Remusat et al. (2004 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₅H₁₈N₄O₄
M _r = 318.33
Triclinic,
a = 8.4860 (4) Å
b = 8.6175 (4) Å
c = 11.7507 (6) Å
α = 77.489 (1)°
β = 81.732 (1)°
γ = 67.977 (1)°
V = 775.83 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 297 K
0.43 × 0.37 × 0.23 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.958, T _max = 0.978
15358 measured reflections
4470 independent reflections
3627 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.173
S = 1.05
4470 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811036300/is2771sup1.cif

e-67-o2606-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811036300/is2771Isup2.hkl

e-67-o2606-Isup2.hkl^{(219KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811036300/is2771Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C7–C12 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O2	0.859 (18)	2.004 (18)	2.6464 (18)	130.9 (15)
N1—H1N1⋯N3ⁱ	0.859 (18)	2.345 (17)	3.0281 (18)	136.7 (15)
C15—H15A⋯O1ⁱⁱ	0.96	2.47	3.346 (2)	151
C1—H1A⋯Cg1ⁱⁱⁱ	0.93	2.90	3.5962 (16)	132

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors wish to express their thanks to Universiti Sains Malaysia (USM), Penang, Malaysia, for providing research facilities. HKF and WSL thank USM for the Research University Grant (1001/PFIZIK/811160). WSL also thanks the Malaysian Government and USM for the award of a research fellowship.

supplementary crystallographic information

Comment

Nitrophenyleneamine is an important class of compounds in organic synthetic chemistry. They are most of the time used to synthesize phenylenediamines by reducing the nitro (NO₂) group to amine (NH₂). Phenylenediamines themselves are then used as composition in making dyes (Sabelle, 2006), metallomesogens (Glebowska et al., 2009) as well as ligand precursors. Condensation of substituted o-phenylenediamine with various diketones is then used in the preparation of a variety of pharmaceuticals (Remusat et al., 2004).

In the title compound (Fig. 1), the 1H-imidazole (C1/C2/N3/C3/N2) is almost planar with a maximum deviation of 0.003 (2) Å at atom C3 and it forms a dihedral angle of 67.12 (8)° with the benzene ring (C7–C12). An S(6) ring motif (Bernstein et al., 1995) is formed via an intramolecular N1—H1N1···O2 hydrogen bond (Table 1).

In the crystal packing (Fig. 2), pairs of intermolecular N1—H1N1···N3 and C15—H15A···O1 hydrogen bonds (Table 1) link the neighbouring molecules to form dimers, leading to the formation of chains along the [021]. The crystal packing is further stabilized by a C—H···π interaction (Table 1), involving the centroid of the benzene ring (Cg1).

Experimental

Ethyl-4-fluro-3-nitro benzoate (4.6 mmol) in dichloromethane (20 mL) was added into the solution of 3-(1H-imidazole-1yl)propane-1-amine (7.0 mmol) and N, N-diisopropylethylamine (5.6 mmol) in dichloromethane (20 mL). The reaction mixture was stirred overnight at room temperature. After completion of the reaction, evidenced by TLC analysis. The reaction mixture was washed with water (10 mL × 2) and 10% Na₂CO₃ (10 ml × 2). The dichloromethane layer was collected and dried over Na₂SO₄. The organic layer was concentrated under reduced pressure to afford white-colored crystals.