Crystals of barium pentacyanonitrosylferrate trihydrate (barium nitroprusside trihydrate), Ba[Fe(CN)(5)(NO)].3H(2)O, have been studied by neutron diffraction in order to examine the structural behaviour of the compound in the 20-120 K temperature range and to determine the structure at 105 K. The results show the existence of a new crystal phase of the compound at 80 K (with a duplicated a parameter), which still exists at 20 K. The crystal structure at 105 K shows a rearrangement of the water molecules, which results in an ordered structure with P1 symmetry. Two of the four independent nitroprusside cations are rotated by 4.5 degrees around the [100] direction.