The stacked two-dimensional supramolecular compound catena-{Co(amp)3Cr(ox)3·6H2O} (amp = 2-picolylamine, ox = oxalate) has been synthesized from the bimolecular approach using hydrogen bonds. It is built from layers in which both Co(amp)(3+) (D) and Cr(ox)(3-) (A) ions are bonded in a repeating DADADA… pattern along the a and c axes by multiple hydrogen bonds. These layers host a well resolved R12 dodecameric discrete ring of water clusters built by six independent molecules located around the 2c centrosymmetric Wyckoff positions of the P21/n space group in which the compound crystallizes. These clusters are ranged along the [001] direction, occupy 733.5 Å(3) (22.0%) of the unit cell and have a chair conformation via 12 hydrogen bonds. The water molecules of the cluster are linked with stronger hydrogen bonds than those between the cluster and its host, which explains the single continuous step of the dehydration process of the compound.