Crystal structure, Hirshfeld surface analysis and PIXEL calculations of a 1:1 epimeric mixture of 3-[(4-nitro-benzyl-idene)amino]-2(R,S)-(4-nitro-phenyl)-5(S)-(propan-2-yl)imidazolidin-4-one.

Ligia R Gomes,James L Wardell,Marcus V N De Souza,John Nicolson Low,Cristiane F Da Costa

doi:10.1107/s2056989019013938

Abstract

A 1:1 epimeric mixture of 3-[(4-nitro-benzyl-idene)amino]-2(R,S)-(4-nitro-phen-yl)-5(S)-(propan-2-yl)imidazolidin-4-one, C19H19N5O5, was isolated from a reaction mixture of 2(S)-amino-3-methyl-1-oxo-butane-hydrazine and 4-nitro-benz-alde-hyde in ethanol. The product was derived from an initial reaction of 2(S)-amino-3-methyl-1-oxo-butane-hydrazine at its hydrazine group to provide a 4-nitro-benzyl-idene derivative, followed by a cyclization reaction with another mol-ecule of 4-nitro-benzaldehyde to form the chiral five-membered imidazolidin-4-one ring. The formation of the five-membered imidazolidin-4-one ring occurred with retention of the configuration at the 5-position, but with racemization at the 2-position. In the crystal, N-H⋯O(nitro) hydrogen bonds, weak C-H⋯O(carbon-yl) and C-H⋯O(nitro) hydrogen bonds, as well as C-H⋯π, N-H⋯π and π-π inter-actions, are present. These combine to generate a three-dimensional array. Hirshfeld surface analysis and PIXEL calculations are also reported.

Highlights

A 1:1 epimeric mixture of 3-[(4-nitrobenzylidene)amino]-2(R,S)-(4-nitrophenyl)5(S)-(propan-2-yl)imidazolidin-4-one, C19H19N5O5, was isolated from a reaction mixture of 2(S)-amino-3-methyl-1-oxobutanehydrazine and 4-nitrobenzaldehyde in ethanol
The product was derived from an initial reaction of 2(S)-amino3-methyl-1-oxobutanehydrazine at its hydrazine group to provide a 4-nitrobenzylidene derivative, followed by a cyclization reaction with another molecule of 4-nitrobenzaldehyde to form the chiral five-membered imidazolidin-4-one ring
As part of our studies on nitrogen-containing heterocyclic compounds, we report the crystal structure, Hirshfeld surface analysis and PIXEL calculations of a 1:1 epimeric mixture of 3-[(4-nitrobenzylidene)amino]-2(R,S)-(4-nitrophenyl)-5(S)(propan-2-yl)imidazolidin-4-one, 1

Summary

Chemical context

Imidazolidin-4-ones have been widely studied (Blackmore & Thompson, 2011) due to their wide range of uses, for example, as chiral ligands in catalysis (Lin et al, 2013; Mondini et al, 2013; Seebach et al, 2008; Puglisi et al, 2013) and for their biological activities (Elrod & Worley, 1999; Gomes et al, 2004; Guerra et al, 2011; Barrow et al, 2007). As a consequence of their utility, there are a number of well-established synthetic routes, in particular those involving chiral synthesis (Blackmore & Thompson, 2011; Eyilcim et al, 2018; Li et al, 2004; Vale et al, 2008, 2009; Catalano et al, 2011; Xu et al, 2010). As part of our studies on nitrogen-containing heterocyclic compounds, we report the crystal structure, Hirshfeld surface analysis and PIXEL calculations of a 1:1 epimeric mixture of 3-[(4-nitrobenzylidene)amino]-2(R,S)-(4-nitrophenyl)-5(S)(propan-2-yl)imidazolidin-4-one, 1

Structural commentary

Intermolecular interactions and contacts

Hirshfeld surface and quantitative analyses of intermolecular interactions

Database survey