Three alkyl-bridged bis(pentadentate) ligands, 1,2-bis[N,N-bis(2-pyridylmethyl)-1,4,7-triazacyclononyl]ethane (tmpdtne), 1,3-bis[N,N’-bis(2-pyridylmethyl)-1,4,7-triazacyclononyl]propane (tmpdtnp), and 1,4-bis[N,N’-bis(2- pyridylmethyl)-1,4,7-triazacyclononyl]butane (tmpdtnb), have been synthesized by reaction of the corresponding bis(tridentate) macrocycles with 2-picolyl chloride at pH similar to 10. Copper(II) complexes of the three ligands have been prepared and were found to have the composition [Cu(2)L](ClO4)(4) . xH(2)O where x = 2 for L = tmpdtne and x = 0 for L = tmpdtnp and tmpdtnb. Single-crystal X-ray diffraction studies established the molecular structure of the monomeric complex, [Cu(dmptacn)](ClO4)(2) (1), where dmptacn = 1,4-bis(2-pyridylmethyl)-1,4,7-triazacyclononane, and the corresponding binuclear complex [Cu-2(tmpdtne)](ClO4)(4) . 2H(2)O (2).