The structures of Co(SCN) and its hydrate Co(SCN)(HO) have been determined using X-ray crystallography. Co(SCN) forms infinite 2D sheets in the mercury(II) thiocyanate structure type, where as Co(SCN)(HO) consists of isolated tetrahedral Co(SCN)(HO) centers and one equivalent of water of crystallization.
The hydrate may be prepared by the salt metathesis reactions, such as the reaction of aqueous cobalt(II) sulfate and barium thiocyanate to produce a barium sulfate precipitate, leaving the hydrate of Co(SCN) in solution:
:CoSO  +  Ba(SCN)  →  BaSO  +  Co(SCN)
or the reaction of the hexakisacetonitrile cobalt(II) tetrafluoroborate and potassium thiocyanate, precipitating KBF
:[Co(NCMe)](BF) + 2KSCN  →  2KBF  +  Co(SCN).
The anhydrate can then be prepared via addition of diethylether as an antisolvent.