N-(3-Chloro-4-methyl­phen­yl)succinamic acid

U Chaithanya; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536812007623

. 2012 Feb 24;68(Pt 3):o835. doi: 10.1107/S1600536812007623

N-(3-Chloro-4-methylphenyl)succinamic acid

U Chaithanya ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3297894 PMID: 22412697

Abstract

In the crystal structure of the title compound, C₁₁H₁₂ClNO₃, the asymmetric unit contains two independent molecules. The N—H bond in the amide segment is anti to the meta-Cl atom in the benzene ring, in both molecules. The amide and carboxyl C=O bonds are also anti to each other and anti to the H atoms on the adjacent –CH₂ groups. Furthermore, the C=O and O—H bonds of the acid group are in syn positions with respect to each other. The dihedral angles between the benzene ring and the amide group are 40.6 (2) and 44.9 (3)° in the two independent molecules. In the crystal, molecules are packed into sheets parallel to the (11-3) plane through O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For our studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2000 ▶); Chaithanya et al. (2012 ▶). For N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶). For N-chloroarylamides, see: Gowda et al. (2003 ▶); Jyothi & Gowda (2004 ▶). For N-bromoarylsulfonamides, see: Usha & Gowda (2006 ▶).

Experimental

Crystal data

C₁₁H₁₂ClNO₃
M _r = 241.67
Triclinic,
a = 6.8788 (9) Å
b = 7.9713 (9) Å
c = 21.119 (3) Å
α = 86.76 (1)°
β = 86.48 (1)°
γ = 79.45 (1)°
V = 1135.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 293 K
0.42 × 0.14 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.875, T _max = 0.974
6890 measured reflections
4066 independent reflections
2649 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.083
wR(F ²) = 0.159
S = 1.26
4066 reflections
303 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.29 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/S1600536812007623/bt5820sup1.cif

e-68-0o835-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812007623/bt5820Isup2.hkl

e-68-0o835-Isup2.hkl^{(199.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812007623/bt5820Isup3.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—H1N⋯O4ⁱ	0.85 (2)	2.05 (2)	2.882 (5)	165 (5)
O3—H3O⋯O2ⁱⁱ	0.83 (2)	1.83 (2)	2.654 (5)	173 (7)
N2—H2N⋯O1ⁱⁱⁱ	0.84 (2)	2.07 (2)	2.891 (5)	165 (5)
O6—H6O⋯O5^iv	0.83 (2)	1.90 (3)	2.703 (5)	164 (7)

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

Acknowledgments

BTG thanks the University Grants Commission, Government of India, New Delhi, for a UGC-BSR one-time grant to faculty.

supplementary crystallographic information

Comment

As part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda et al., 2000; Chaithanya et al., 2012), N-(aryl)-methanesulfonamides (Gowda et al., 2007), N-chloroarylsulfonamides (Gowda et al., 2003; Jyothi & Gowda, 2004) and N-bromoarylsulfonamides (Usha & Gowda, 2006), in the present work, the crystal structure of N-(3-Chloro-4-methylphenyl)succinamic acid has been determined (Fig. 1). The asymmetric unit of the structure contains two independent molecules. The conformations of the N—H bonds in the amide segments are anti to the meta–chloro atoms in the benzene rings of both the molecules, in contrast to the syn conformation observed between the N—H bond and ortho–chloro atom in N-(2-Chloro-4-methylphenyl)-succinamic acid (I) (Chaithanya et al., 2012).

Further, the conformations of the amide oxygen and the carboxyl oxygen of the acid segments are anti to each other and both are anti to the H atoms on the adjacent –CH₂ groups.

The C═O and O—H bonds of the acid groups are in syn position to each other, similar to that observed in (I).

The dihedral angles between the phenyl ring and the amide group in the two independent molecules are 40.58 (22)° and 44.93 (27)°, compared to the value of 48.39 (12)° in (I).

In the structure, the pairs of O—H···O and N—H···O intermolecular hydrogen bonds pack the molecules into infinite chains (Table 1, Fig.2).

Experimental

The solution of succinic anhydride (0.01 mole) in toluene (25 ml) was treated dropwise with the solution of 3-chloro,4-methylaniline (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 3-chloro-4-methyl- aniline. 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 of the solvent at room temperature.