Divalent copper coordination polymers containing aliphatic dicarboxylate and bis(3-pyridylmethyl)piperazine (3-bpmp) tethering ligands exhibit different topologies depending on the length of the polymethylene chain and stoichiometric ratio. {[Cu(succinate)(3-bpmp)]·8H 2 O} n (1) and {[Cu(adipate)(3-bpmp)(H 2 O)]·10H 2 O} n (4) both display (4,4) rhomboid grids, although the latter shows significant undulations to accommodate the additional girth of the dicarboxylate tethers. [Cu 2 (succinate) 2 (3-bpmp) 0.5 (H 2 O)] n (2) and [Cu 2 (glutarate) 2 (3-bpmp)] n (3) possess {Cu 2 (OCO) 3 } partial paddlewheel and {Cu 2 (OCO) 4 } complete paddlewheel carboxylate bridged dimeric units, respectively. However, 2 has a (6,3) brick-layered structure with a rare binodal moganite (mog) supramolecular topology, while 3 possesses a non-interpenetrated primitive cubic network. Intriguing co-crystallized water tapes are seen in 1 and 4. Thermal dehydration and decomposition behavior of 1–4 is also presented.