Ethyl (Z)-3-(4-methyl­anilino)-2-[(4-methyl­phen­yl)carbamo­yl]prop-2-enoate

Arun M Islor; B Garudachari; Thomas Gerber; Eric Hosten; Richard Betz

doi:10.1107/S1600536812043723

. 2012 Oct 27;68(Pt 11):o3218. doi: 10.1107/S1600536812043723

Ethyl (Z)-3-(4-methylanilino)-2-[(4-methylphenyl)carbamoyl]prop-2-enoate

Arun M Islor ^a, B Garudachari ^a, Thomas Gerber ^b, Eric Hosten ^b, Richard Betz ^b,^*

PMCID: PMC3515303 PMID: 23284523

Abstract

The title compound, C₂₀H₂₂N₂O₃, is a secondary amine featuring an amide and an ester functionality in connection with a Michael system. The conformation about the C=C bond is E. Intramolecular N—H⋯O hydrogen bonds occur. In the crystal, C—H⋯O contacts connect the molecules into chains along the b-axis direction.

Related literature

For general information about the synthetic and industrial importance of aniline and its derivatives, see: Berry & Royd (1984 ▶); Garudachari et al. (2012 ▶); Sridharan et al. (2006 ▶); Kasthuri et al. (2008 ▶). For graph-set analysis of hydrogen bonds, see: Etter et al. (1990 ▶); Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₀H₂₂N₂O₃
M _r = 338.40
Monoclinic,
a = 18.8170 (4) Å
b = 11.9752 (3) Å
c = 15.6043 (4) Å
β = 91.470 (1)°
V = 3515.07 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 200 K
0.42 × 0.26 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.965, T _max = 0.984
16569 measured reflections
4353 independent reflections
3411 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.147
S = 1.05
4353 reflections
237 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.56 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2010 ▶); cell refinement: SAINT (Bruker, 2010 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Click here for additional data file.^{(25.1KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812043723/zq2185sup1.cif

e-68-o3218-sup1.cif^{(25.1KB, cif)}

Click here for additional data file.^{(2.7KB, cdx)}

Supplementary material file. DOI: 10.1107/S1600536812043723/zq2185Isup2.cdx

Click here for additional data file.^{(213.4KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812043723/zq2185Isup3.hkl

e-68-o3218-Isup3.hkl^{(213.4KB, hkl)}

Click here for additional data file.^{(6.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812043723/zq2185Isup4.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
C23—H23⋯O1ⁱ	0.95	2.68	3.620 (2)	170
C25—H25⋯O2ⁱⁱ	0.95	2.70	3.4685 (19)	139
N1—H1⋯O1	0.97 (2)	1.85 (2)	2.6383 (17)	135.9 (18)
N2—H2⋯O2	0.88 (2)	1.92 (2)	2.6713 (18)	143.0 (19)

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

Acknowledgments

AMI is thankful to the Department of Atomic Energy, Board for Research in Nuclear sciences, Government of India, for the Young Scientist award.

supplementary crystallographic information

Comment

The study of aniline derivatives is important due to the presence of amines in natural products and nucleic acids (Berry & Royd, 1984). Aniline compounds find widespread applications in the field of synthetic chemistry such as the synthesis of quinolines and indoles (Garudachari et al., 2012; Sridharan et al., 2006). Aniline derivatives are also widely used in many industries such as in the production of dyes and agrochemicals (Kasthuri et al., 2008). Keeping in mind the importance of aniline derivatives, the title compound was synthesized to study its crystal structure.

The molecule can – simultaneously – be regarded as a secondary amide, an enamine, an ester as well as featuring a Michael system. The C=C bond is (E) configured. The least-squares planes defined by the respective carbon atoms of the phenyl rings intersect at an angle of 49.57 (8) °. The central part of the molecule, including the ethyl group, is essentially planar (r.m.s. of the least-squares plane defined by all the non-hydrogen atoms of the respective part of this molecule = 0.0569 Å) with the oxygen atom of the ethoxy group deviating most from this plane (0.095 (1) Å) (Fig. 1).

In the crystal, intramolecular N–H···O bonds involving all secondary amine groups and double bonded oxygen atoms are observed. In addition, intermolecular C–H···O contacts whose range falls slightly below the sum of van-der-Waals radii of the atoms participating are present. The latter contacts are supported by hydrogen atoms on the phenyl group that is bonded to the amide-type nitrogen atom and exclusively have ketonic oxygen atoms as acceptors. In terms of graph-set analysis (Etter et al., 1990; Bernstein et al., 1995), the descriptor for these contacts is S(6)S(6)R²₂(14)R²₂(18) on the unary level. Metrical parameters as well as information about the symmetry of these contacts are summarized in Table 1. In total, the molecules are connected to chains along the crystallographic b axis. The shortest intercentroid distance between two aromatic systems was measured at 4.5754 (9) Å and is observed between the two different aromatic moieties in neighbouring molecules (Fig 2).

The packing of the title compound in the crystal structure is shown in Figure 3.

Experimental

A mixture of diethyl-{[(4-methylphenyl)amino]methylidene}propanedioate (1.0 g, 0.0036 mol) and 4-methylaniline (0.19 g, 0.0018 mol) in dowtherm (10 ml) was stirred at 150 °C for 2 h. The reaction mixture was then cooled to 25 °C and stirred in n-hexane (20 ml) for 10 min. The solid product obtained was filtered, dried and further purified by column chromatography using petrol ether and ethyl acetate (v:v = 5:5) as the eluent to get a white solid. Crystals were grown by slow evaporation of a dilute ethanol solution at room temperature, yield: 0.52 g (42.6%).