The self-assembly of supramolecular metallacycles via the coordination-driven directional bonding approach can be modified to produce some unexpected structural variations. The combination of a flexible ligand-capped dinuclear transition-metal acceptor like [Cu-2(dppm)(2)(NCMe)(2)]X-2 (1X(2); dppm = Ph2PCH2PPh2; X- = BF4-, PF6-, or BPh4-) with monodentate-bidentate donors like 2-, 3-, and 4-pyridylcarboxylates produced oligomeric compounds [{Cu-2(dppm)(2)}(mu-(2-PyCO2))](2)X-2 (2X(2)), [{Cu-2(dppm)(2)}(mu-(3-PyCO2))](2)X-2 (3X(2)) and [{Cu-2(dppm)(2)}(mu-(4-PyCO2))](4)X-4 (4X(4)), respectively, as the thermodynamically stable products in one-pot reactions. However, the modified self-assembly is still subject to steric hindrance. The reaction of complex 1(BF4)(2) with 6-Me-3-PyCO2H did not produce a polygonal dimeric metallacycle but a simple dinuclear complex, [Cu-2(dppm)(2)(6-Me-3-PyCO2)](BF4) (5(BF4)). The crystal structures of complexes 2(PF6)(2), 3(PF6)(2), 4(BF4)(4), and 5(BF4) were determined using X-ray diffraction.