The synthesis of coordination networks with pre-calculated architectures is an important challenge in the design of molecular solids. We discuss some of the basic underlying geometrical principles involved when constructing uniform networks and relate them to recent successes that we have had with multifunctional mixed ligand systems. Exploitation of mixed ligand bonding about a metal center of known coordination geometry is a versatile approach towards the identification of novel network topologies and the generation of supramolecular isomerism. Specifically, we utilize the bispyridyl/acetylacetonate copper(II) chromophore to grow metal-organic coordination polymers which exhibit supramolecular isomerism. Additionally, the hitherto unknown 8,3-a 3-D co-ordination network was synthesized as one of three concomitant supramolecular isomers. The 8,3-a network yields optically active single crystals with 58% void space despite undergoing 4 fold interpenetration.