Because non-covalent contacts are important to the design and construction of materials with functional applications, efforts that seek to uncover chemical features responsible for the assembly of multi-molecular arrays hold current interest. The building-block approach is one strategy that has been successfully employed for the construction of molecular assemblies. By designing molecular components with complementary functional groups, the construction of predictable supramolecular motifs is possible. Although various modes of molecular alignment have been generated using this strategy, the extension of low dimensional motifs (discrete and 1-D patterns) to 2- and 3-D patterns remain a current challenge.

Hexamethylenetetramine (HMTA) holds promise as a component for forming useful supramolecular architectures. Due to the hydrogen bond ability and tetrahedral arrangement of the four nitrogen atoms of HMTA, we envisioned that cocrystallization with various hydrogen bond donors could form extended molecular networks. As a means to explore the crystal chemistry of HMTA, we have prepared several bimolecular and coordination compounds using HMTA as the fundamental building-block. Inspection of the crystal structures of these materials and the Cambridge Structural Database provides key information towards understanding the packing tendencies of this unique and potentially useful supramolecular synthon.