A study of the polymorphism of 4-methyl-2-nitroacetanilide and related compounds

Abstract

The full crystal structures of three polymorphs of 4-methyl-2-nitroacetanilide (MNA) are described. The white form (MNA-l), is the most stable form. The least stable form is the amber farm (MNA-2). The yellow form (MNA-3) has been found to change in a topotactic manner into the white form. The relationships between the three polymorphs are discussed and possible mechanisms to account for the topotactic phase changes are presented. The polymorphs show different i.r. and Raman spectra in the solid state. These spectra, and those of deuterated analogues are interpreted and their differences explained. A study of the proton and 13-C n.m.r. spectra show that the conformation of flexible MNA molecules is markedly dependent on the nature of the solvent. The ability of other o-nitroacetanilides to exist in a white (intermolecular) and yellow (intramolecular hydrogen bonded) forms has been examined. Finally, details of the synthesis of these compounds and an account of the examination of MNA polymorphs by differential scanning calorimetry (d.s.c) are described. A description of computer programs used, including one in BASIC which will enable the contents of unit cell(s) to be viewed, is given.