To provide an atomic level insight into the changes in bonding upon heating into the liquid state X-ray total scattering experiments were performed on the crystalline ABX3 structures. Variable temperature total scattering measurements were carried out on [TBuA][Mn(dca)3] and [TPnA][Mn(dca)3] from 34 °C to 258 °C (i.e. below Td in each case) to determine changes in local structure.