Five new crystalline phases from coordination compounds containing copper(II) ethylenediamine and iodine (F1-F5) were obtained and identified by Single Crystal X-Ray Diffraction (SCXRD). The compounds present a coordination environment where the four nitrogen atoms are located in a square planar geometry and two apical positions complete an octahedron with different degrees of distortion from the ideal geometry. These two opposite vertices are occupied by one iodide and one water molecule in F1 or two iodide ligands in F2-F5. The compounds can easily be synthesized and undergo several transformations that were monitored and studied. A comparative study of the crystal packing was performed to understand the stability of the different phases.