AbstractThe solvate complexes that can be obtained by either dissolving metal iodides in N,N-dimethylformamide (DMF) or by synthesising them in DMF have the general composition [M(DMF)x]Iy. DMF shows to behave as simple monodentate ligand with low sterical impact, so that x in the composition follows the radius of My+. We present here the crystal structures of the alkaline earth and lanthanoid metal iodide complexes [Mg(DMF)6]I2, [Ca(DMF)6]I2, [Sr(DMF)7]I2, [Ba(DMF)8]I2, [La(DMF)9]I3, [Ln(DMF)8]I3 (isotypic series for Ln = Nd, Sm, Eu, Dy, Gd, Er, Yb and Lu) and for the tris-triiodide complex salt [Sc(DMF)6](I3)3. Their different crystal structure types can be compared on the basis of the packing topologies of the nearly spherical cationic entities which show simple sphere packing motifs.