In this work we explore the overall structural behaviour of the [(CH3)2NH2][Mn(HCOO)3] multiferroic compound across the temperature range where its ferroelectric transition takes place by means of calorimetry, thermal expansion measurements and variable temperature powder and single crystal X-ray diffraction. The results clearly proof the presence of structural phase transition at Tt ~187 K (temperature at which the dielectric transition occurs) that involves a symmetry change from R-3c to Cc, twinning of the crystals, a discontinuous variation of the unit cell parameters and unit cell volume, and a sharp first-order-like anomaly in the thermal expansion. In addition, the calorimetric results show a 3-fold order-disorder transition. The calculated pressure dependence of the transition temperature is rather large (dTt/dP = 4.6 $pm$ 0.1 K/kbar), so that it should be feasible to shift it to room temperature using adequate thermodynamic conditions, for instance by application of external pressure.
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