Phase Transitions and Crystal Structures of Ni(II) Complexes Determined with X-ray Powder Diffraction Data

Structural changes of chloride and bromide complexes, [Ni(Et(2)en)(2)(H2O)(2)]Cl-2 (designated as 1a) and [Ni(Et(2)en)(2)]Br-2 (2a), have been investigated by using simultaneous measurements of powder X-ray diffraction (XRD) and differential scanning calorimetry data under the temperature and humidity controls. The hydrate form of chloride complex 1a was transformed into an anhydrate form (1b) by heating at a temperature of 361 K. Then the 1b was reversibly returned to the original 1a by humidification at 25% relative humidity (RH) and temperature of 300 K. On the other hand, the anhydrate form of the bromide complex 2a was first transformed into a hydrate form (2b) at 30% RH and 300 K. On heating, the 2b turned to a new anhydrate form (2c) at 344 K, and then it returned to the original form 2a on further heating. In the present experiments, a series of reactions of 2a proceeded via 2c, which was newly found with the benefit of differential scanning calorimetry (DSC) measurements performed in parallel to the XRD measurements. Crystal structures of new crystalline forms of 1b, 2b, and 2c were determined from the powder XRD data.