Calorimetric Study of Correlated Disordering in [Hdamel]₂[Cu^II(tdpd)₂]·2THF Crystal

The heat capacity of [Hdamel]2[CuII(tdpd)2]·2THF was measured from 6 to 250 K by adiabatic calorimetry. There are four heat anomalies around 150 K associated with disordering in the orientation of the uncoordinated THF molecules and in the conformation of the out-of-plane allyl groups of [Hdamel]+ units. The total entropy of transition was determined to be 19.8 J K−1 mol−1, less than the 4R ln 2 (R = gas constant) expected from the crystal structure at room temperature. The smallness of the total entropy change on phase transitions proves the presence of the strong motional correlation between the adjacent allyl groups. The calorimetric conclusion agreed with the crystal structure at 200 K re-examined in this study.