Methyl 2-(4-chloro-3,5-dinitro­benz­amido)­acetate

Xiang-Xiang Wu; Xue-Fen Wu; Yi-Min Hou; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811050446

. 2011 Nov 30;67(Pt 12):o3486. doi: 10.1107/S1600536811050446

Methyl 2-(4-chloro-3,5-dinitrobenzamido)acetate

Xiang-Xiang Wu ^a, Xue-Fen Wu ^a, Yi-Min Hou ^a, Seik Weng Ng ^b,^c, Edward R T Tiekink ^b,^*

PMCID: PMC3239110 PMID: 22199958

Abstract

The title molecule, C₁₀H₈ClN₃O₇, is twisted with the dihedral angle between the amide and benzene ring being 38.75 (11)°. The C—N—C—C torsion angle between the amide and acetyl groups is −150.1 (2)°. Finally, each nitro group is twisted out of the plane of the benzene ring to which it is connected [O—N—C—C torsion angles = 34.0 (3) and −64.5 (3)°]. Linear supramolecular chains along [010] and mediated by N—H⋯O hydrogen bonds between successive amide groups dominate the crystal packing. The chains are consolidated into the three-dimensional structure by C—H⋯O contacts.

Related literature

For biological and crystal engineering studies of related compounds, see: Liu et al. (2009 ▶); Eissmann & Weber (2011 ▶).

Experimental

Crystal data

C₁₀H₈ClN₃O₇
M _r = 317.64
Orthorhombic,
a = 14.5219 (5) Å
b = 4.7949 (2) Å
c = 18.5368 (6) Å
V = 1290.74 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.906, T _max = 0.967
4743 measured reflections
2258 independent reflections
2134 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.074
S = 1.08
2258 reflections
194 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.25 e Å⁻³
Absolute structure: Flack (1983 ▶), 725 Friedel pairs
Flack parameter: −0.05 (6)

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: X-SEED (Barbour, 2001 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811050446/hg5145sup1.cif

e-67-o3486-sup1.cif^{(16.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050446/hg5145Isup2.hkl

e-67-o3486-Isup2.hkl^{(111KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811050446/hg5145Isup3.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
N1—H1⋯O3ⁱ	0.88 (1)	1.99 (1)	2.833 (3)	163 (3)
C1—H1a⋯O7ⁱⁱ	0.98	2.59	3.460 (3)	148
C3—H3a⋯O6ⁱⁱⁱ	0.99	2.53	3.502 (3)	169
C3—H3b⋯O2^iv	0.99	2.42	3.380 (3)	162
C10—H10⋯O5^v	0.95	2.37	3.223 (3)	149

Open in a new tab

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

Acknowledgments

We thank Henan University of Traditional Medicine and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Molecules related to the title compound, (I), attract interest for their biological properties (Liu et al., 2009) and also in terms of crystal engineering endeavours (Eissmann & Weber, 2011). In (I), Fig. 1, the dihedral angle between the amide (O3,N1,C4) atoms and the benzene ring is 38.75 (11)°. The acetyl group is also twisted out of the plane of the amide group with the C4—N1—C3—C2 torsion angle being -150.1 (2)°. Each nitro group is twisted out of the plane of the benzene ring to which it is connected with the O4—N2—C7—C6 torsion angle = 34.0 (3)° and with O6—N3—C9—C8 = -64.5 (3)°.

The crystal packing is dominated by the formation of linear supramolecular chains along the b axis and mediated by N—H···O hydrogen bonds involving the amide group, Fig. 2 and Table 1. Chains are consolidated in the crystal packing by C—H···O interactions, Fig. 3 and Table 1.

Experimental

To a solution of 4-chloro-3,5-dinitrobenzoic acid (0.48 g, 2 mmol) in dichloromethane (30 ml) was added 1-ethyl-3-(3-dimethylaminopropyl)carbodiimidehydrochloride (0.40 g, 2.1 mmol) and N,N-dimethylaminopyridine (25 mg, 0.2 mmol). The mixture was stirred at room temperature for an hour. Methyl 2-aminoacetate (178 mg, 2 mmol) in chloroform (20 ml) along with several drops of triethylamine were added. After another six hours, the mixture was subjected to chromatography (petroleum ether/acetone 4:1) to provide the product as a yellow solid (501.5 mg, 80% yield). Crystals were grown from a mixture of dichloromethane and n-hexane (1:1 v/v).