The hydrothermal reaction of Cu(OAc) 2 .H 2 O with thiophene-2,5-dicarboxylic acid (H 2 tdc) and 4,4 ' -bipyridine (bpy) gave a copper(II) coordination polymer {[Cu(tdc)(bpy)(H 2 O)](bpy)} n (1), in which the (4,4) layers are assembled via strong hydrogen bonds between the aqua ligands and the uncoordinated carboxylate oxygen atoms into a porous 3-D molecular architecture with parallelogrammic channels. The guest bpy molecules reside in the channels, involving intermolecular C-H...N hydrogen bonds with the host framework, can be removed upon heating at reduced pressure.