Here, we report a unique transformation from heterochiral to homochiral structures in ionic crystals composed of complex cations and complex anions. Treatment of an anionic (Au3Co2III)-Co-I complex, Lambda Lambda-[Au3Co2(D-pen)(6)](3-) ([1](3-); H(2)pen = penicill-amine), with M = Mn-II, Co-II, Ni-II, Zn-II in water in the presence of 1,10-phenanthroline (phen) commonly gave ionic crystals formulated as [M(phen)(2) (H2O)(2)] [Na(H2O)(6)]-[{M(phen)(2) (H2O)}(1)](3) (2(M)), in which [M(phen)(2)(H2O)(2)](2+) and [M(phen)(2)(H2O)](2+) adopt Delta and Lambda configurations, respectively. While 2(co), 2(Ni ), and 2(zn) were all stable in each mother liquor, 2(Mn) was converted to [Mn(phen)(3)](3)[1](2)- phen (3(Mn)) containing the A configurational [Mn(phen)(3)](3+) under the same conditions. 3(Mn )showed a water adsorption capacity higher than that of 2(Mn), despite its lower porosity of crystal.