The simple nickel(II) acetate/H3L system (H3L = 2-(2-hydroxyphenyl)-1,3-bis[4-(2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imi dazolidine) presents an unusually complicated reactivity scheme, which strongly depends on the Ni(OAc)(2)/H3L molar ratio and on the pH of the medium. Thus, in addition to the formerly reported compounds [Ni2L(OAc)(H2O)(2)[Ni2L(OAc)-(H2O)(HOAc)]center dot 3.25H(2)O, 1. 3.25H(2)O; [{Ni3L(OAc)(OH)(H2O)(MeOH)(2)}(CO3){Ni2L(OAc)(MeOH)(2)}]center dot 2.7H(2)O center dot 1.5MeOH, 2 center dot 2.7H(2)O center dot 1.5MeOH; and [Ni3L(OAC)(2)(OH)(H2O)(MeOH)(2)]center dot 3H(2)O center dot 0.5MeOH, 3 center dot 3H(2)O center dot 0.5MeOH, this system can also yield some other complexes as [Ni2L(o-O-C6H4-CHO)(H2O)center dot 1.75H(2)O, 4. 1.75H(2)O; [Ni2L(OH)(H2O)(MeOH)]center dot 3H(2)O center dot 1.5MeOH, 5. 3H(2)O center dot 1.5MeOH; [Ni2L(OAc)(MeOH)2]center dot H2O center dot 3MeOH, 6. H2O center dot 3MeOH; and [{Ni2L(MeOH)}(CO3){Ni2L(MeOH)(2)}]center dot 4.75H(2)O center dot 2MeOH, 7. 4.75H(2)O center dot 2MeOH. A detailed study of the reaction scheme that allows obtaining all of these complexes is presented herein, as well as the structural characterization of the novel compounds 4. 1.75H(2)O to 7. 4.75H(2)O-2MeOH. X-ray analyses show that all of them present stereoisomery in the solid state. In this way, 6. H2O center dot 3MeOH appears particularly interesting, as its molecular and supramolecular chirality is only controlled by hydrogen bonds. Magnetic studies of 5. 3H(2)O to 7. 4.75H(2)O center dot 2MeOH are also discussed, and the complicated magnetic superexchange pathway shown by 7. 4.75H(2)O center dot 2MeOH is analyzed in light of DFT calculations.