4-[(4-Acetyl­phen­yl)amino]-2-methyl­idene-4-oxo­butanoic acid

B Narayana; Prakash S Nayak; Balladka K Sarojini; Jerry P Jasinski

doi:10.1107/S1600536814012562

. 2014 Jun 7;70(Pt 7):o752–o753. doi: 10.1107/S1600536814012562

4-[(4-Acetylphenyl)amino]-2-methylidene-4-oxobutanoic acid

B Narayana ^a, Prakash S Nayak ^b, Balladka K Sarojini ^c, Jerry P Jasinski ^d,^*

PMCID: PMC4120591 PMID: 25161547

Abstract

In the title compound, C₁₃H₁₃NO₄, the N—C(=O) bond length of 1.354 (2) Å is indicative of amide-type resonance. The dihedral angle between the mean planes of the benzene ring and oxoamine group is 36.4 (3)°, while the mean plane of the 2-methylidene group is inclined by 84.2 (01)° from that of the oxoamine group. In the crystal, classical O—H⋯O hydrogen bonds formed by the carboxylic acid groups and weak N—H⋯O weak interactions formed by the amide groups and supported by weak C—H⋯O interactions between the 2-methylidene, phenyl and acetyl groups with the carboxylic acid, oxoamine and acetyl O atoms, together link the molecules into dimeric chains along [010]. The O—H⋯O hydrogen bonds form R ₂ ²(8) graph-set motifs.

Related literature

For the pharmacological activity of amide derivatives, see: Galanakis et al. (2004 ▶); Kumar & Knaus (1993 ▶); Ban et al. (1998 ▶); Ukrainets et al. (2006 ▶), Lesyk & Zimenkovsky (2004 ▶); Gududuru et al. (2004 ▶). For related structures, see: Nayak et al. (2013a ▶,b ▶). For standard bond lengths, see: Allen et al. (1987 ▶). graphic file with name e-70-0o752-scheme1.jpg

Experimental

Crystal data

C₁₃H₁₃NO₄
M _r = 247.24
Triclinic,
a = 5.0164 (5) Å
b = 5.2908 (4) Å
c = 21.8464 (18) Å
α = 92.833 (6)°
β = 90.315 (7)°
γ = 96.222 (7)°
V = 575.67 (8) Å³
Z = 2
Cu Kα radiation
μ = 0.89 mm⁻¹
T = 173 K
0.42 × 0.22 × 0.12 mm

Data collection

Agilent Eos Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO and CrysAlis RED; Agilent, 2012 ▶) T _min = 0.756, T _max = 1.000
3374 measured reflections
2168 independent reflections
1934 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.134
S = 1.05
2168 reflections
176 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SUPERFLIP (Palatinus et al., 2012 ▶); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814012562/zl2589sup1.cif

e-70-0o752-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814012562/zl2589Isup2.hkl

e-70-0o752-Isup2.hkl^{(119.2KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814012562/zl2589Isup3.cml

CCDC reference: 1005968

Additional supporting information: 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—H3⋯O2ⁱ	0.97 (5)	1.66 (5)	2.6262 (17)	174 (4)
N1—H1⋯O1ⁱⁱ	0.88	2.29	3.1039 (17)	154
C5—H5B⋯O2ⁱⁱⁱ	1.00 (3)	2.48 (3)	3.434 (2)	160 (2)
C7—H7⋯O1ⁱⁱ	0.95	2.56	3.254 (2)	130
C13—H13A⋯O4^iv	0.98	2.50	3.465 (2)	167

Open in a new tab

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

Acknowledgments

BN thanks the UGC for financial assistance through a BSR one-time grant for the purchase of chemicals. PSN thanks Mangalore University for research facilities and DST–PURSE financial assistance. JPJ acknowledges the NSF–MRI program (grant No. CHE-1039027) for funds to purchase the X-ray diffractometer.

supplementary crystallographic information

S1. Comment

Amide bonds play a major role in the elaboration and composition of biological systems, which are the main chemical bonds that link amino acid building blocks together to give proteins. Amide bonds are not limited to biological systems and are indeed present in a huge array of molecules, including major marketed drugs. Amide derivatives possessing anti-inflammatory (Galanakis et al., 2004; Kumar et al., 1993; Ban et al., 1998), antimicrobial (Ukrainets et al., 2006), anti-tubercular (Lesyk et al., 2004) and antiproliferative (Gududuru et al., 2004) activities are reported in the literature. Crystal structures of some amide derivatives related to the title compound include, viz., 4-(4-iodoanilino)-2-methylene-4-oxobutanoic acid and 4-(3-fluoro-4-methylanilino)-2-methylidene-4-oxobutanoic acid (Nayak et al., 2013a,b). Hence in view of its potential pharmacological importance, the title compound 4-[(4-acetylphenyl)amino]-2-methylidene-4-oxobutanoic acid, C₁₃H₁₃NO₄, was synthesized from 3-methylidenedihydrofuran-2,5-dione with good yields and its crystal structure is reported here.

In the title compound, The C=C bond is present as its anti-Saytzeff tautomer. The N–C(=O) bond length of 1.354 (2)A (A) is indicative of amide-type resonance (Fig. 1). All other bond lengths are in normal ranges (Allen et al., 1987). In the crystal, classical O—H···O hydrogen bonds formed by the carboxylic groups and N—H···O weak intermolecular interactions formed by the amide groups and supported additionally by weak C—H···O intermolecular interactions between the 2-methylidene, phenyl and acetyl groups with the carboxylic, oxoamine and acetyl oxygen atoms (Table 1), together link the molecules into dimeric chains along [0 1 0] (Fig. 2). The O—H···O hydrogen bonds form R₂²(8) graph-set motifs. The dihedral angle between the mean planes of the phenyl ring (C6–C10) and oxoamine group (C1/C2/O1/N1) is 36.4 (3)°, while the mean plane of the 2-methylidene group (C2–C5) is further inclined by 84.2 (1)° from that of the oxoamine group.

S2. Experimental

3-Methylidenedihydrofuran-2,5-dione (0.112 g, 1 mmol) was dissolved in a 30 ml acetone and stirred at ambient temperature. 4-Aminoacetophenone (0.135 g, 1 mmol) in 20 mL acetone was added over 30 mins (Fig. 3). After sirring for 1.5 h the slurry was filtered. The solid was washed with acetone and dried to give the title compound, C₁₃H₁₃NO₄. Single crystals were grown from methanol and toluene (1:1) mixture by the slow evaporation method (yield. 0.248 g, 87.32%, m.p.: 461–463 K).