In this paper, a detailed study on the gelation properties of a series of terpyridine and dipyrazine-pyridine ligands in the presence of metal salts is reported. To reveal the driving forces for the self-assembly of the metallogelators, their crystal structure is scrutinized. Inspired by the gelation of CuCl2[Terpy-nCN], where "Terpy-nCN" is 4'-(n-cyanophenyl)-2,2',6',2 ''-terpyridine, to look into the aggregation behavior of the related analogues, synthesis of CuCl2[Dipyz-py-nCN] derivatives, where "Dipyz-py-nCN" is 4-(n-cyanophenyl)-2,6-di-pyrazin-2-yl-pyridine, with the same cyano groups is performed. We then find that the Dipyz-py counterpart forms crystals when the molecules are stacked in an alternating way, instead of the unidirectional one required for gel formation. A crystal engineering approach is applied to determine the interactions that are favorable for fabricating a fiber network that is likely to be present in both crystalline and gel states and to find the interaction that disturbs this delicate balance between gelation and crystallization in coordination compounds; then, we conclude that the subtle balance between the molecular shape and intermolecular interactions is the origin of the gelation and crystallization of the current molecular system. This enables us to find the mutual connection among the structure of molecules, assembly behavior, and intermolecular interactions. With our experiments, a deep understanding of the balance among solution, gelation, and crystallization with subtle molecular diversions is provided.