Molecular adducts of 2,4-diamino-6-methyl-1,3,5-triazine (1) have been prepared with various aliphatic dicarboxylic acids. The molecular complexes (1a-1i) thus formed by co-crystallizing 1 with oxalic, malonic, succinic, fumaric, acetylene dicarboxylic, glutaric, thiodiglycolic, diglycolic, and adipic acids have been found to give two types of host-guest assemblies that have voids or channels in a three-dimensional arrangement. The different types of host-guest arrangement appear to result from differences in the acidity of the dicarboxylic acids, that is, acids with pK(a) < 3.0 give host networks that consist of 1 and the corresponding acid with water or solvent molecules of crystallization present as guests, whereas acids with pK(a) > 3.0 exist as guests in voids in a host network formed by 1. The former arrangement is observed in adducts 1a, 1b, 1c, and 1h and the latter arrangement is found in adducts 1c, 1d, 1f, 1g and 1i.