The use of a strategy combining ligand design and changes of reaction conditions has been investigated with the goal of directing the assembly of mononuclear, dinuclear, tetranuclear, and polymeric copper(H) complexes. As a result, closely related copper monomers, alkoxo dimers, and hydroxo cubanes, along with a carbonate-bridged polymeric species, have been synthesized using the rigid, aliphatic amino ligands cis-3,5-diamino-transhydroxycyclohexane (DAHC), cis-3,5-diamino-trans-methoxycyclohexane (DAMC), and the glutaryl-linked derivative glutaric acid bis-(cis-3,5-diaminocyclohexyl) ester (GADACE). The composition of the monomeric complex has been determined by X-ray crystallography as [Cu(DAHC)(2)](ClO4)(2) (1), the two dimers as [{ Cu(DAHC)(OMe)}(2)]-(ClO4)(2)(MeOH)-Me-. (2) and [{Cu(DAMC)(OMe)(ClO4)}(2)] (3), the three Cu4O4 cubanes as [{Cu(DAHC)(OH)}(4)](ClO4)(4)(.) 2.5MeOH (4), [{Cu(DAMC)(OH)}(4)](ClO4)(4)-H2O (5), and [{CU2(OH)(2)(GADACE)}(2)]Cl(4)(.)2MeOH(.)6H2O (6), and an infinite-chain structure as [{Cu(DAHC)(CO3)}(n)] (7). Furthermore, the cubane structures 4 and 5 have been investigated magnetically. Our studies indicate that formation of the monomeric, dimeric, and tetranuclear DAHC and DAMC complexes can be controlled by small changes in reaction conditions and that further preorganization of the ligand moiety by linking the DAHC cores (GADACE) allows more effective direction of the self-assembly of the CU4O4 cubane core.