Pyrazinamide (PZA) is among the first-line drugs for the treatment of tuberculosis, which seems to reappear as a frequent disease. In this study we investigate the structural changes induced in these samples as evidenced by thermal behaviour and electron spin resonance of new transition metal complexes of PZA. We is search for a correlation between structure and thermal transformations described as multi-step processes consisting in crystalline phase transition, decomposition, melting and thermo-oxidation.