Rational Assembly of Primitive Cubic Networks Using Hexameric Stacks of Sodium Aryloxides as Nodes

The two sodium aryloxide complexes [{(4-R−C6H4ONa)6·(dioxane)3}∞], 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.