N-(3,4-Dimethyl­phen­yl)succinamic acid

B Thimme Gowda; Sabine Foro; B S Saraswathi; Hartmut Fuess

doi:10.1107/S1600536810002084

. 2010 Jan 23;66(Pt 2):o436. doi: 10.1107/S1600536810002084

N-(3,4-Dimethylphenyl)succinamic acid

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

PMCID: PMC2979820 PMID: 21579851

Abstract

The asymmetric unit of the title compound, C₁₂H₁₅NO₃, contains two independent molecules. In both molecules, the conformations of the amide oxygen and the carbonyl O atom of the acid segment are anti to the adjacent CH₂ groups. In the crystal, both molecules form inversion dimers linked by pairs of O—H⋯O hydrogen bonds and N—H⋯O interactions link the dimers into [100] chains.

Related literature

For the crystal structures of related anilides, see: Gowda et al. (2007 ▶); Gowda, Foro, Saraswathi & Fuess (2009 ▶); Gowda, Foro, Saraswathi et al. (2009 ▶). For the modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ▶); Jagannathan et al. (1994 ▶).

Experimental

Crystal data

C₁₂H₁₅NO₃
M _r = 221.25
Triclinic,
a = 9.736 (1) Å
b = 9.919 (1) Å
c = 12.601 (2) Å
α = 106.42 (1)°
β = 100.98 (1)°
γ = 99.81 (1)°
V = 1112.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 299 K
0.44 × 0.40 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.959, T _max = 0.985
7776 measured reflections
4538 independent reflections
3173 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.118
S = 1.03
4538 reflections
305 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.17 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 datablocks I, global. DOI: 10.1107/S1600536810002084/rz2408sup1.cif

e-66-0o436-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810002084/rz2408Isup2.hkl

e-66-0o436-Isup2.hkl^{(222.3KB, 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
O3—H3O⋯O5ⁱ	0.85 (2)	1.82 (2)	2.6681 (18)	174 (2)
N1—H1N⋯O4ⁱⁱ	0.894 (18)	2.127 (18)	2.9909 (18)	162.5 (15)
O6—H6O⋯O2ⁱ	0.88 (2)	1.78 (2)	2.6555 (18)	175 (2)
N2—H2N⋯O1	0.87 (2)	2.26 (2)	3.0676 (19)	154.7 (17)

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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

As a part of studying the effect of the ring and side chain substitutions on the crystal structures of anilides (Gowda et al., 2007; Gowda, Foro, Saraswathi & Fuess, 2009; Gowda, Foro, Saraswathi et al., 2009), we report herein the crystal structure of N-(3,4-dimethylphenyl)succinamic acid (I). The asymmetric unit of (I) contains two independent molecules (Fig. 1). The conformations of the N—H and C═O bonds in the amide segments are anti to each other. Further, the conformation of the amide oxygen and the carbonyl oxygen of the acid segment are anti to the H atoms of their adjacent CH₂ groups, while the conformation of the C=O and O—H bonds of the acid group are in syn position to each other, similar to that observed in N-(3,4-dichlorophenyl)succinamic acid monohydrate (II) (Gowda, Foro, Saraswathi & Fuess, 2009) and N-(2,6-dimethylphenyl)succinamic acid (III) (Gowda, Foro, Saraswathi et al., 2009).

The conformation of the amide hydrogen in (I) is syn to the meta-methyl group in the benzene ring, contrary to the anti conformation observed between the amide hydrogen and the meta-Cl in (II). Further, the conformation of the amide oxygen and the carbonyl oxygen of the acid segment are syn to each other, contrary to the anti conformation observed in (II). N—H···O and O—H···O intermolecular hydrogen bonds pack the molecules into chains running parallel to the a axis (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

A solution of succinic anhydride (0.02 mol) in toluene (25 ml) was treated dropwise with a solution of 3,4-dimethylaniline (0.02 mol) 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 the completion of reaction. The mixture was then treated with dilute hydrochloric acid to remove the unreacted 3,4-dimethylaniline. The resultant solid N-(3,4-dimethylphenyl)succinamic acid 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 by elemental analysis and characterized by its infrared and NMR spectra. The rod like colourless single crystals used in X-ray diffraction studies were grown by slow evaporation at room temperature of an ethanolic solution.