Ethyl 5-(4-amino­phen­yl)isoxazole-3-carboxyl­ate

Jun-Tao Zhao; Jing-Jing Qi; You-Jun Zhou; Jia-Guo Lv; Ju Zhu

doi:10.1107/S1600536812010653

. 2012 Mar 17;68(Pt 4):o1111. doi: 10.1107/S1600536812010653

Ethyl 5-(4-aminophenyl)isoxazole-3-carboxylate

Jun-Tao Zhao ^a, Jing-Jing Qi ^a, You-Jun Zhou ^a, Jia-Guo Lv ^a,^*, Ju Zhu ^a

PMCID: PMC3344059 PMID: 22589968

Abstract

The asymmetric unit of the title compound, C₁₂H₁₂N₂O₃, contains two molecules in which the benzene and isoxazole rings are almost coplanar, the dihedral angles between their mean planes being 1.76 (9) and 5.85 (8)°. The two molecules interact with each other via N—H⋯N and N—H⋯O hydrogen bonds, which link the molecules into layers parallel to the ac plane. The layers stack in a parallel mode with an interlayer distance of 3.36 (7) Å.

Related literature

For the synthesis and biological activity of soxazoles, see; Silva et al. (2002 ▶); Changtam et al. (2010 ▶); Patel et al. (2010 ▶); Barceló et al. (2007 ▶); Yamamoto et al. (2007 ▶); Mao et al. (2010 ▶). For their structure–activity relationships, see: Andrzejak et al. (2011 ▶); Becht et al. (2006 ▶); Veronese et al. (1997 ▶). For our research in this area, see: Qi et al. (2011 ▶).

Experimental

Crystal data

C₁₂H₁₂N₂O₃
M _r = 232.24
Triclinic,
a = 7.591 (2) Å
b = 11.303 (4) Å
c = 13.818 (4) Å
α = 88.155 (4)°
β = 87.008 (4)°
γ = 86.233 (4)°
V = 1181.0 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.15 × 0.09 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T _min = 0.986, T _max = 0.992
4901 measured reflections
4074 independent reflections
2636 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.122
S = 0.98
4074 reflections
308 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 1999 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812010653/bv2198sup1.cif

e-68-o1111-sup1.cif^{(27.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812010653/bv2198Isup2.hkl

e-68-o1111-Isup2.hkl^{(199.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812010653/bv2198Isup3.cdx

Supplementary material file. DOI: 10.1107/S1600536812010653/bv2198Isup4.cml

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—H3C⋯N2ⁱ	0.86	2.44	3.243 (3)	157
N3—H3B⋯O6ⁱⁱ	0.86	2.62	3.396 (2)	150
N1—H1B⋯N4	0.86	2.44	3.255 (3)	159
N1—H1A⋯O3ⁱⁱⁱ	0.86	2.63	3.394 (3)	149

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

Acknowledgments

The authors are grateful to the Second Military Medical University for supporting this study. J-TZ thanks Dr Zhen-Xia Chen for helpful discussions.

supplementary crystallographic information

Comment

Isoxazoles are important compounds possessing pharmaceutical properties. Extensive investigation on the crystal structures of isoxazoles helps disclose their structure-activity relationship (Veronese et al. (1997); Becht et al. (2006); Andrzejak et al. (2011)). In a continuation of our research (Qi et al. (2011)), herein, we report the crystal structure of the title isoxazole derivative. The asymmetric unit of the title compound, C₁₂H₁₂N₂O₃, contains two planar molecules. In the molecular structure, (I) (Fig. 1), the dihedral angle between the isoxazole ring C7/C8/C9/N2/O1 and phenyl ring C1/C2/C3/C4/C5/C6 is 1.76 (9)° for molecule 1. The amino-group of the benzene ring is nearly into the same plane (r.m.s. deviation = 0.034 Å) as is usual for amino groups attached to aromatic rings. The COOEt group of the isoxazole ring is also in the same plane. The dihedral angle between the carboxylate and the isoxazole ring is 0.92 (13)°. For molecule 2, the dihedral angle for the isoxazole ring C19/C20/C21/N4/O4 and phenyl ring C13/C14/C15/C16/C17/C18 is 5.85 (8)°, which is slightly larger than molecule 1. The carboxylate group also has a little distortion with the larger dihedral angle between the carboxylate and the isoxazole ring being 1.58 (11)°. The two molecules interact with each other by strong N—H···N and N—H···O hydrogen bonds, which link the molecules into a layer (Fig. 2, Table 1). The layers then stack in parallel mode with the interlayer distance of 3.36 (7) Å.

Experimental

After a reaction of 4-nitroacetophenone and diethyl oxalate in a basic solution of ethanol for 2hrs, then add acetic acid to neutralize the solution from former reaction to obtain yellow solids. The solids were collected and reacted with hydroxylamine hydrochloride in ethanol at reflux for 4 hrs to form yellow products which were then reduced with stannous chloride in ethyl acetate to yield the title compound.