Linkage isomers trans-bis(N-propyl-1,2-diaminoethane)dinitronickel(II) (brown, 1), trans-bis(N-isopropyl-1,2-diaminoethane)dinitritonickel(II) (blue-violet, 2a) and trans-bis(N-isopropyl-1,2-diaminoethane)dinitronickel(II) (brown, 2b) have been synthesized from solution and X-ray single crystal structure analysis of complex (1) has been performed. Simultaneous TG-DTA analyses reveal that complex (1) exhibits two successive phase transitions before to undergo decomposition (initial temperature of decomposition, Ti = 215 °C). The first one is reversible (82-98 °C; ΔH = 1.75 kJ mol -1 for heating and 93-77 °C; ΔH = -1.65 kJ mol-1 for cooling) and the second one is irreversible endothermic (135-150 °C kJ mol-1; ΔH = 1.80 kJ mol-1) phase transition. No visual color changes are observed in any of the two transitions. The causes related to the first phase transition remain unexplored. However, on the basis of IR spectral studies the second phase transition is supposed to be due to conformational changes of the diamine chelate rings. On the other hand, complexes (2a) and (2b) undergo decomposition without showing any phase transition [Ti = 185 and 195 °C for (2a) and (2b), respectively]. © Springer 2007.