Three small organic molecular co-crystal compounds (C3N6H6)·(C6H10O4)·H2O(1), C3H8N2O(3) and (H4btec)2·(4,4′-bipy)(4)(H4btec=1,2,4,5-benzenetetracarboxylic acid, 4,4′-bipy=4,4′-bipyridine) and one coordination supramolecular compound [Mn(C2O4)(H2O)2]·C6H11NO2(2) were synthesized by hydrothermal reaction. They were characterized by elemental analysis, infrared(IR) spectroscopy and single crystal X-ray diffraction(XRD). Structural analyses reveal that these 2D or 3D supramolecular networks of the compounds were formed by $$C---H \cdots O$$ , $$N---H \cdots O$$ , $$N---H \cdots N$$ , $$O---H \cdots O$$ and $$O---H \cdots N$$ hydrogen bonds. Therein, the functional groups of -COOH, -NH2 and -OH play important roles in constructing supramolecular architectures.