Four new one-dimensional (1D) polymeric complexes, {[Cu4(L1)2(µ-Br)2(µ4-CO3)]Br(ClO4)3·3H2O}n(1), {[Cu2L2(µ-Cl)Cl2] (ClO4)2·H2O}n(2), {[Cu2L3(µ-Cl)2](ClO4)2}n(3), and {[Cu2L4(µ-Cl)2](ClO4)2}n(4), have been synthesized and characterized, where L1= N,N,N′,N′-tetrakis(3′-aminopropyl)-1,3-propylenediamine, L2= N,N,N′,N′-tetrakis(2′-aminoethyl)-1,3-propylenediamine, L3= N,N,N′,N′-tetrakis(2′-aminoethyl)-1,4-butylenediamine, L4= N,N,N′,N′-tetrakis(2′-aminoethyl)-1, 6-hexylenediamine. X-Ray structure analysis revealed that the polymeric complexes, created by the bridging groups which are exhibited in the formula, present different 1D coordination motifs: double-stranded chains with voids of 43.5 Å2for 1, sigmoid chains for 2, zigzag chains for 3and 4with different coordination polyhedra. Various hydrogen bonding interactions such as N–HCl, N–HO, C–HCl, N–HBr and O–HBr join the polymeric chains to generate two-dimensional networks with bigger voids. Magnetic susceptibility data were fitted according to the molecular structures using Hamiltonians: H= −2J1(S2S3+ S1S4) − 2J2(S2S1) − 2J3(S1S3+ S2S4) − 2J4(S3S4), which corresponds to a rectangular array of spins for 1, and H= −2JS1S2corresponds to a dinuclear array of spins for 2, 3and 4. It was found that the coupling constants of 1are −60, −113, −54 and −11 cm−1, and those of 2, 3, and 4are −2.46, −1.56 and −0.15 cm−1, respectively. [ABSTRACT FROM AUTHOR]