N-(3,5-Dimethyl­phen­yl)succinamic acid

B S Saraswathi; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536810053055

. 2010 Dec 24;67(Pt 1):o234. doi: 10.1107/S1600536810053055

N-(3,5-Dimethylphenyl)succinamic acid

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

PMCID: PMC3050227 PMID: 21522734

Abstract

In the title compound, C₁₂H₁₅NO₃, the N—H and C=O bonds are anti to each other. The C=O and O—H bonds of the acid group display an antiperiplanar orientation relative to each other. The crystal packing features a three-dimensional network of molecules held together by O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For our study of the effect of ring and side-chain substitutions on the crystal structures of anilides, see: Gowda et al. (2009 ▶ 2010a ▶,b ▶). For modes of interlinking carboxylic acids by hydrogen bonds, see: Leiserowitz (1976 ▶). The packing of molecules involving dimeric hydrogen-bonded association of each carboxyl group with a centrosymmetrically related neighbor has also been observed, see: Jagannathan et al. (1994 ▶).

Experimental

Crystal data

C₁₂H₁₅NO₃
M _r = 221.25
Monoclinic,
a = 14.346 (2) Å
b = 5.0225 (9) Å
c = 17.860 (3) Å
β = 112.00 (2)°
V = 1193.2 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.45 × 0.08 × 0.05 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.961, T _max = 0.996
4452 measured reflections
2419 independent reflections
1593 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.147
S = 1.03
2419 reflections
153 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 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/S1600536810053055/bt5440sup1.cif

e-67-0o234-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053055/bt5440Isup2.hkl

e-67-0o234-Isup2.hkl^{(118.9KB, 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
N1—H1N⋯O2ⁱ	0.88 (2)	2.01 (2)	2.881 (2)	171 (2)
O3—H3O⋯O1ⁱⁱ	0.86 (3)	1.77 (3)	2.630 (2)	172 (3)

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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 ring and side chain substitutions on the crystal structures of anilides (Gowda et al., 2009, 2010a,b), in the present work, the crystal structure of N-(3,5-dimethylphenyl)- succinamic acid (I) has been determined. The conformations of N—H and C═ O bonds in the amide segment are anti to each other (Fig. 1). The conformation of the amide oxygen and the carbonyl oxygen of the acid segment are anti to each other, similar to the anti conformation observed in N-(2,6-dimethylphenyl)-succinamic acid (II) (Gowda et al., 2009), but in contrast to the the syn conformation observed in N-(3-methylphenyl)succinamic acid (III) (Gowda et al., 2010a) and N-(3,4-dimethylphenyl)- succinamic acid (IV) (Gowda et al., 2010b).

But, the conformations of the amide oxygen and the carbonyl oxygen of the acid segment are anti to the adjacent –CH₂ groups in the above compounds. The conformation of the amide hydrogen is syn to one of the meta–methyl groups in the benzene ring and anti to the other.

Further, the C═O and O—H bonds of the acid group in (I) are in anti position to each other, in contrast to the syn conformation observed in (II), (III) and (IV).

The intermolecular O—H···O and N—H···O hydrogen bonds pack the molecules into a three-dimensional network (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 3,5-dimethylaniline (0.01 mole) also in toluene (20 ml) with constant stirring. The resulting mixture was stirred for about one h 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 3,5-dimethylaniline. The resultant solid N-(3,5-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.

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