N-(4-Chloro-2-methyl­phen­yl)maleamic acid

K Shakuntala; Viktor Vrábel; B Thimme Gowda; Jozef Kožíšek

doi:10.1107/S1600536811047817

. 2011 Nov 16;67(Pt 12):o3317. doi: 10.1107/S1600536811047817

N-(4-Chloro-2-methylphenyl)maleamic acid

K Shakuntala ^a, Viktor Vrábel ^b, B Thimme Gowda ^a,^*, Jozef Kožíšek ^b

PMCID: PMC3238967 PMID: 22199816

Abstract

In the molecular structure of the title compound, C₁₁H₁₀ClNO₃, the conformation of the N—H bond in the amide segment is syn to the ortho-methyl group in the phenyl ring. The C=O and O—H bonds of the acid group are in the relatively rare anti position with respect to each other. This is an obvious consequence of the hydrogen bond donated to the amide carbonyl group. The central oxobutenoic acid core C(=O)—C=C—C—OH is twisted by 31.65 (6)° out of the plane of the 4-chloro-2-methylphenyl ring. An intramolecular O—H⋯O hydrogen bond occurs. In the crystal, N—H⋯O hydrogen bonds link the molecules into infinite chains running along the a axis.

Related literature

For studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2000 ▶, 2010 ▶); Prasad et al. (2002 ▶), on N-(aryl)-methanesulfonamides, see: Jayalakshmi & Gowda (2004 ▶), on N-(aryl)-arylsulfonamides, see: Shetty & Gowda (2005 ▶) and on N-chloroarylsulfonamides, see: Gowda & Kumar (2003 ▶). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ▶)

Experimental

Crystal data

C₁₁H₁₀ClNO₃
M _r = 239.65
Orthorhombic,
a = 12.1310 (11) Å
b = 7.3990 (7) Å
c = 25.466 (2) Å
V = 2285.7 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 295 K
0.45 × 0.35 × 0.25 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.865, T _max = 0.918
17740 measured reflections
1819 independent reflections
1642 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.089
S = 1.02
1819 reflections
154 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); 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: DIAMOND (Brandenburg, 2002 ▶); software used to prepare material for publication: SHELXL97, PLATON (Spek, 2009 ▶) and WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047817/bq2317sup1.cif

e-67-o3317-sup1.cif^{(16.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047817/bq2317Isup2.hkl

e-67-o3317-Isup2.hkl^{(89.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047817/bq2317Isup3.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	0.86 (1)	2.10 (1)	2.9556 (19)	174 (2)
O2—H2A⋯O1	0.92 (1)	1.57 (1)	2.4797 (17)	171 (3)

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Symmetry code: (i) Inline graphic .

Acknowledgments

VV and JK thank the VEGA Grant Agency of the Slovak Ministry of Education (1/0679/11) and the Research and Development Agency of Slovakia (APVV-0202–10) for support and the Structural Funds, Interreg IIIA, for financial support in purchasing the diffractometer. VZR thanks the University Grants Commission, Government of India, New Delhi, for the award of an RFSMS research fellowship.

supplementary crystallographic information

Comment

The amide moiety is the constituent of many biologically significant compounds. As part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda et al., 2000, 2010), N-(aryl)-methanesulfonamides (Jayalakshmi & Gowda, 2004), N-(aryl)-arylsulfonamides (Shetty & Gowda, 2005) and N-chloroarylsulfoamides (Gowda & Kumar, 2003), in the present work, the crystal structure of N-(4-chloro-2-methylphenyl)-maleamic acid (I) has been determined (Fig.1).

The conformations of the N—H and the C=O bonds in the amide segment are anti to each other. But the conformation of the N—H bond is syn to the ortho-methyl group in the phenyl ring. In the maleamic acid moiety, the amide C=O bond is anti to the adjacent C—H bond, while the carboxyl C=O bond is syn to the adjacent C—H bond. The observed rare anti conformation of the C=O and O—H bonds of the acid group is similar to that observed in N-(2-methylphenyl)-maleamic acid (Gowda et al., 2010). This is an obvious consequence of the hydrogen bond donated to the amide carbonyl group. The central oxobutenoic acid core C(=O)—C=C—C—OH is twisted by 31.65 (6)° out of the plane of the 4-chloro-2-methylphenyl ring. The C2–C3 bond length of 1.333 (2)Å clearly indicates the double bond character.

The various modes of interlinking carboxylic acids by hydrogen bonds is described elsewhere (Leiserowitz, 1976).

In (I), both the intramolecular O–H···O and intermolecular N–H···O hydrogen bonds have been observed. The packing of molecules linked by N—H···O hydrogen bonds into infinite chains running along the a-axis is shown in Fig. 2.

Experimental

The solution of maleic anhydride (0.025 mol) in toluene (25 ml) was treated dropwise with the solution of 4-chloro-2-methylaniline (0.025 mol) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about 30 min. and set aside for an additional 30 min. at room temperature for the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 4-chloro-2-methylaniline. The resultant solid N-(4-chloro-2-methylphenyl)-maleamic acid was filtered under suction and washed thoroughly with water to remove the unreacted maleic anhydride and maleic acid. It was recrystallized to constant melting point from ethanol. The purity of the compound was checked by elemental analysis and characterized by its infrared spectra.

The plate like colorless single crystals of the title compound used in X-ray diffraction studies were grown in an ethanol solution by slow evaporation (0.5 g in about 30 ml of ethanol) at room temperature.