This work introduces the use of 8-aminoquinoline subcomponents to generate complex three-dimensional structures. Together with a tris(formylpyridine), 8-aminoquinoline condensed around ZnII templates to produce a tris(tridentate) ligand. This ligand is incorporated into either a tricapped trigonal prismatic ZnII9L6 structure or a pair of pseudo-octahedral ZnII6L4 diastereomers, with S4 and D2 symmetries. Introduction of a methyl group onto the aminoquinoline modulated the coordination sphere of ZnII, which favored the ZnII9L6 structure and disfavored the ZnII6L4 assembly. The tricapped trigonal prismatic ZnII9L6 architecture converted into a single ZnII6L4 cage diastereomer following the addition of a dianionic 4,4'-dinitrostilbene-2,2'-disulfonate guest. Four of these guests clustered tightly at the four windows of the ZnII6L4 cage, held in place through electrostatic interactions and hydrogen bonding, stabilize a single diastereomeric configuration with S4 symmetry.