Cobalt(II) iodide crystallizes in two polymorphs, the α- and β-forms.
The α-polymorph consists of black hexagonal crystals, which turn dark green when exposed to air.
Under a vacuum at 500 °C, samples of α-CoI2 sublime, yielding the β-polymorph as a yellow crystals.
The hexaaquo salt consists of separated [Co(H2O)6]2+ and iodide ions as verified crystallographically.
[3][4] Anhydrous cobalt(II) iodide is sometimes used to test for the presence of water in various solvents.