Initial attempts to make [Ni(H2O)2(15-crown-5)](NO3)2, i.e. to insert the Ni2+ ion into the 15-crown-5 macrocycle, gave the mono- (two polymorphs) and dihydrate of a co-crystal of[Ni(H2O)6](NO3)2 and 15-crown-5 (1,4,7,10,13-pentaoxacyclopentadecane=15C5). Synthetic routes designed to restrict the water available to the Ni2+ cation gave three additional compounds, [Ni(H2O)6](NO3)2-trans-[Ni(H2O)4(MeOH)2]-(NO3)2x2(15C5), cis-[Ni(H2O)4(NO3)2]-trans-[Ni(H2O)4-(NO3)2]x2(15C5) and [Ni(H2O)2(MeCN)(NO3)2]x15C5x-MeCN. All five compounds contain Ni2+ ions with two trans aqua ligands. In all six structures these aqua ligands make hydrogen bonds to the 15C5 molecules to form stacks in which the Ni complexes and 15C5 molecules alternate. The structures are surprisingly complicated: all are co-crystals,some are also solvates, and most have Z0 > 1. The target compound was finally prepared by heating pale green crystals of [Ni(H2O)6](NO3)2x15C5x2H2O to over 350 K and then cooling the resulting mixture of yellow crystals and solution to room temperature. Formation of the target compound seems to be favored at higher temperatures by a positive Delta(rxn)S(o) and an increased rate of ligand exchange.