A neutral, non-interpenetrated porous metal–organic framework (MOF) having (10,3)-a topology, Cu(3,5-PDC)(DMF)(py), (DMF = N,N′-dimethylformamide, py = pyridine), has been constructed via the assembly of the achiral tri-connected building blocks 3,5-pyridinedicarboxylate (3,5-PDC) and CuN(CO2)2, synthesized in situ. Similarly, a 2D structure having (6,3) topology has been generated, each by means of terminal co-ligand directed synthesis.