The properties of the intermolecular hydrogen bonds in the monoclinic (Form I) and the orthorhombic (Form II) polymorphs of paracetamol, C₈H₉NO₂, have been studied by single crystal polarized Raman spectroscopy (40 to 3700 cm⁻¹) in a wide temperature range (5 K < T < 300 K) in relation to the dynamics of methyl-groups of the two forms. A detailed analysis of the temperature dependence of the wavenumbers, bandwidths and integral intensities of the spectral bands has revealed an essential difference between the two polymorphs in the strength and ordering of OH⋯O and NH⋯O hydrogen bonds. The compression of intermolecular hydrogen bonds is interrelated with crystal packing and the dynamics of methyl-groups. On structural compression of the orthorhombic polymorph on cooling, a compromise is to be sought between the shortening of OH⋯O and NH⋯O bonds, attractive CH⋯O and repulsive CH⋯H contacts in the crystal structure. As a result of a steric conflict at temperatures below 100 K, N–H⋯O hydrogen bonds become significantly disordered, and an extended intramolecular transition from the conformation “staggered” with respect to the CO bond to the one “staggered” with respect to the NH bond is observed. In most of the studied crystals this transition was only about 60% complete even at 5 K, but in some of the crystals the orientation of all the methyl-groups became staggered with respect to the NH bond at low temperatures. This complete transition was coupled to a sharp shortening of the OH⋯O and NH⋯O hydrogen bonds at <100 K, the appearance of new additional positions of the protons in these H-bonds, and a slight strengthening of the C–H⋯O bonds formed by methyl-groups. The same conformational transition has been observed also in the monoclinic polymorph at T < 80 K. The crystal packing in Form I prevents the O–H⋯O hydrogen bonds from adopting the optimum geometry, and they are significantly disordered at all the temperatures, especially at ≤200 K. The packing of molecules in Form I is also not favourable to form C–H⋯O hydrogen bonds involving methyl-groups. One can conclude from the comparison of diffraction and spectroscopic data that the higher stability of Form I results not from a larger strength of individual OH⋯O and NH⋯O hydrogen bonds, but is a cumulative effect: all the hydrogen bonds together stabilize the structure of the monoclinic polymorph more than that of the orthorhombic polymorph.

The effect of carboxylic acids on glycine polymorphism, salt and co-crystal formation was compared for slow evaporation of solutions at ambient conditions, spray drying, “fast” and “slow” anti-solvent crystallisation and dry co-grinding. Different phases were found to crystallise from the same starting components, depending on the preparative technique. Small amounts of most carboxylic acids (glutaric acid being the only exception) promoted crystallisation of the γ-polymorph in solution and as a result of co-grinding. When added in equimolar quantities, the same carboxylic acids formed salts with glycine (addition of glutaric acid resulted in co-crystal formation) on slow evaporation of solutions and on co-grinding. Neither succinic nor L-malic acids produced glycine salts, but instead promoted formation of γ-glycine when present in any amount. Anti-solvent crystallisation and spray drying of solutions containing small or large amounts of carboxylic acids produced a variety of glycine polymorphs as both pure phases and their mixtures, whereas only oxalic acid yielded salts. The ability to synthesise glycinium semi-oxalate form II by spray drying was demonstrated.

The strontium ferrite radiation-thermal synthesis process due to heating by intensive electron beam is described. The radiation-thermal and thermal strontium ferrite synthesis processes kinetics were studied and compared.