(S)-1-Methoxy­carbonyl-2-(4-nitro­phen­yl)ethanaminium chloride

Xiao-Chun Wen

doi:10.1107/S1600536808020874

. 2008 Jul 12;64(Pt 8):o1460. doi: 10.1107/S1600536808020874

(S)-1-Methoxycarbonyl-2-(4-nitrophenyl)ethanaminium chloride

Xiao-Chun Wen ^a,^*

PMCID: PMC2962090 PMID: 21203174

Abstract

The title compound, C₁₀H₁₃N₂O₄ ⁺·Cl⁻, comprises a Cl⁻ anion and a protonated aminium cation. The crystal packing is stabilized by cation–anion N—H⋯Cl hydrogen bonds and N—H⋯O hydrogen bonds, building an infinite two-dimensional network parallel to the (001) plane. The S absolute configuration at the chiral center was deduced from the synthetic pathway and confirmed by the X-ray analysis.

Related literature

For details of α-amino acid derivatives as precursors for the synthesis of novel biologically active compounds, see: Lucchese et al. (2007 ▶); Arki et al. (2004 ▶); Hauck et al. (2006 ▶); Dai et al. (2008 ▶); Azim et al. (2006 ▶).

Experimental

Crystal data

C₁₀H₁₃N₂O₄ ⁺·Cl⁻
M _r = 260.67
Monoclinic,
a = 4.825 (3) Å
b = 8.426 (3) Å
c = 15.111 (9) Å
β = 95.64 (4)°
V = 611.4 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.32 mm⁻¹
T = 298 (2) K
0.25 × 0.18 × 0.17 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.931, T _max = 0.942
6215 measured reflections
2751 independent reflections
2077 reflections with I > 2σ(I)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.112
S = 1.03
2751 reflections
154 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 1259 Friedel pairs
Flack parameter: −0.03 (9)

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808020874/dn2364sup1.cif

e-64-o1460-sup1.cif^{(16.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808020874/dn2364Isup2.hkl

e-64-o1460-Isup2.hkl^{(135KB, hkl)}

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
N2—H11B⋯O4ⁱ	0.89	2.31	2.929 (4)	127
N2—H11B⋯Cl1ⁱ	0.89	2.71	3.380 (3)	133
N2—H11C⋯Cl1ⁱⁱ	0.89	2.42	3.175 (3)	143
N2—H11A⋯Cl1	0.89	2.34	3.151 (3)	151

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

Acknowledgments

This work was supported by a Start-up Grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

α-Amino acid derivatives are important molecules due to their pharmacological properties. Recently, there has been an increased interest in the enantiomeric preparation of α-amino acid derivatives as precursors for the synthesis of novel biologically active compounds (Lucchese et al., (2007); Arki et al., (2004); Hauck et al., (2006); Azim et al., (2006); Dai et al., (2008)). Here we report the crystal structure of the title compound.

The title compound is built up from a Cl^- anion and a protonated amino group cation (Fig. 1). The nitro group and the benzene ring are nearly planar, they are only twisted to each other by a torsion angles of C2-C1-N1-O1 (2.1 (7)° ) and C6-C1-N1-O2 (4.4 (7)° ), and the methyl 2-aminopropanoate substituent group is a zig-zag chain.

The crystal packing is stabilized by cation-anion N—H···Cl H-bonds and N—H···O H-bonds building an infinite two-dimensional network developping parallel to the (0 0 1) plane.(Table 1, Fig. 2).

The S absolute configuration at C8 is deduced from the synthetic pathway and confirmed by the X-ray analyses.

Experimental

Under nitrogen protection, 2-amino-3-phenylpropanoic acid (30 mmol), nitric acid (50 mmol) and sulfuric acid (20 mmol) were added in a flask. The mixture was stirred at 110 °C for 3 h. The resulting solution was poured into ice water (100 mL), then filtered and washed with distilled water. The nitration amino acid was esterified with H₂SO₄ and CH₃OH at 110 °C for 12 h, the crude product was obtained by evaporated the solution, and then recrystallized with distilled water by adding 1 ml HCl to yield colorless block-like crystals, suitable for X-ray analysis.