The design, synthesis and application of polytopic ligands to crystal engineering using metal coordination and hydrogen bonding will be presented. We have synthesized ligands incorporating pyridine, pyrimidine, pyrazine and triazine moieties. A variety of one-, two- and three-dimensional coordination networks were characterized following coordination of the ligands with inorganic salts primarily silver and copper salts. In contrast, hydrogen-bonded networks and capsules were formed following self-assembly of the ligands with polyphenols and carboxylic acids.