The two sodium aryloxide complexes [{(4-R-C6H4ONa)(6).(dioxane)(3)}(infinity)], where R = Et (1) or F (2), have been prepared and found to form three-dimensional cubic networks in the solid state. Each structure is similarly composed of dioxane-connected Na6O6 aggregates that act as octahedral nodes in directing the assembly process. Although the localized metrical parameters within the hexameric cages are similar to each other, as well as to those of the molecular analogue [(4-F-C6H4ONa)(6).(THF)(8)] (3), the gross architectures show significant variations. In particular, the smaller complex 2 ensures effective filling of space through transannular Na-F interaggregate interactions, resulting in substantial compression of the cubic framework.