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Solid polymorphism of four compounds of the type [M(NH 3 ) 6 ](XY 4 ) 2  , where M = Co 2+  or Cd 2+  , and XY 4  = ClO 4  -  or BF 4  -  has been studied at 100 -300 K by DSC. One or two phase transitions of the investigated compounds have been found. For the compounds with M = Co the phase transitions have not yet been described in the literature. For the compounds with M = Cd the phase transition-temperature is in good agreement with the results obtained by NMR and EPR. Generally, for [M(NH 3 ) 6 ](BF 4 ) 2  compounds (M = Mg, Fe, Co, or Ni) the phase transition temperature T Cl  is lower than that for the corresponding [M(NH 3 ) 6 ](ClO 4 ) 2  , but for compounds with M = Cd it is higher. However, the enthalpy and entropy changes at the T CI  phase transitions of [M(NH 3 ) 6 ](BF 4 ) 2  are always lower than those for [M(NH 3 ) 6 ](ClO 4 ) 2 . Moreover, for the compounds of this type a correlation between the transition temperature T Cl  and the crystal lattice parameter a has been found.

DSC Investigations of the Phase Transitions of [M(NH 3 ) 6 ](ClO 4 ) 2 and [M(NH 3 ) 6 ](BF 4 ) 2 , where M = Co and Cd