N-(2,5-Dichloro­phen­yl)succinamic acid

B S Saraswathi; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811028297

. 2011 Jul 23;67(Pt 8):o2093. doi: 10.1107/S1600536811028297

N-(2,5-Dichlorophenyl)succinamic acid

B S Saraswathi ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3213535 PMID: 22091112

Abstract

In the title compound, C₁₀H₉Cl₂NO₃, the conformation of the N—H bond in the amide segment is syn with respect to the ortho-Cl atom and anti to the meta-Cl atom of the benzene ring. In the crystal, intermolecular O—H⋯O and N—H⋯O hydrogen bonds pack the molecules into two types of chains along the a and b axes, respectively, leading to an overall sheet structure. The acid group in the side chain is disordered and was refined using a split model with site-occupation factors of 0.60:0.40.

Related literature

For our studies of the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Bhat & Gowda (2000 ▶); Gowda et al. (2007 ▶); Saraswathi et al. (2011a ▶,b ▶), on N-(aryl)-methanesulfonamides, see: Jayalakshmi & Gowda (2004 ▶) and on N-chloro-arylsulfonamides, see: Gowda et al. (2003 ▶). For the modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ▶). For the packing of molecules involving dimeric hydrogen-bonding associations of each carboxyl group with a centrosymmetrically related neighbor, see: Jagannathan et al. (1994 ▶).

Experimental

Crystal data

C₁₀H₉Cl₂NO₃
M _r = 262.08
Monoclinic,
a = 5.726 (1) Å
b = 4.787 (1) Å
c = 41.583 (6) Å
β = 91.93 (2)°
V = 1139.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 293 K
0.44 × 0.16 × 0.09 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.791, T _max = 0.951
3375 measured reflections
2046 independent reflections
1552 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.077
wR(F ²) = 0.171
S = 1.14
2046 reflections
185 parameters
54 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.75 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811028297/vm2110sup1.cif

e-67-o2093-sup1.cif^{(17KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811028297/vm2110Isup2.hkl

e-67-o2093-Isup2.hkl^{(100.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811028297/vm2110Isup3.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
O2A—H2A⋯O3Aⁱ	0.82	1.90	2.687 (15)	162
O2B—H2B⋯O3Bⁱ	0.82	1.90	2.64 (2)	150
N1—H1N⋯O1ⁱⁱ	0.85 (2)	2.07 (2)	2.901 (6)	167 (5)

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

Acknowledgments

BSS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

supplementary crystallographic information

Comment

The amide and sulfonamide moieties are important constituents of many biologically important compounds. As a part of our studies on the effects of substituents on the structures and other aspects of this class of compounds (Bhat & Gowda, 2000; Gowda et al., 2003, 2007; Jayalakshmi & Gowda, 2004; Saraswathi et al., 2011a,b), in the present work, the crystal structure of N-(2,5-dichlorophenyl)-succinamic acid (I) has been determined (Fig. 1). The conformation of the N—H bond in the amide segment is syn to the ortho–chloro atom and anti to the meta–chloro atom of the benzene ring, similar to the syn conformation observed between the amide hydrogen and the ortho- methyl group and anti conformation between the amide hydrogen and the meta-methyl group in the benzene ring of N-(2,5-dimethylphenyl)-succinamic acid monohydrate (II) (Saraswathi et al., 2011a).

Further, the conformations of the amide oxygen and the carboxyl oxygen of the acid segment are syn to each other. But the conformation of the amide C═O is anti to the H atoms on the adjacent –CH₂ group, while the carboxyl C═O is syn to the H atoms on the adjacent –CH₂ group.

The C═O and O—H bonds of the acid group are in syn position to each other, similar to that observed in (II) and in N-(2,6-dichlorophenyl)-succinamic acid (Saraswathi et al., 2011b).

The intermolecular O—H···O and N—H···O hydrogen bonds, along a- and b-axes, respectively, pack the molecules into infinite chains in the structure (Table 1, Fig.2).

The modes of interlinking carboxylic acids by hydrogen bonds is described elsewhere (Leiserowitz, 1976). The packing of molecules involving dimeric hydrogen bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed (Jagannathan et al., 1994).

Experimental

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated dropwise with the solution of 2,5-dichloroaniline (0.01 mole) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about one hour and set aside for an additional hour at room temperature for completion of the reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 2,5-dichloroaniline. The resultant title compound was filtered under suction and washed thoroughly with water to remove the unreacted succinic anhydride and succinic acid. It was recrystallized to constant melting point from ethanol. The purity of the compound was checked and characterized by its infrared and NMR spectra.

Needle like colorless single crystals used in X-ray diffraction studies were grown in ethanolic solution by slow evaporation at room temperature.