Three new members of the copper sulfate/heterocyclic diamine family [Cu(4,4'-bpy)(H2O)(3)-(SO4)]. 2H(2)O (1; 4,4'-bpy = 4,4'-bipyridine), [Cu(bpe)(2)][Cu(bpe)(H2O)(2)(SO4)(2)]. 2H(2)O (2; bpe = trans-1,2-bis(4-pyridyl)ethylene), and [Cu(bpe)(H2O)(SO4)] (3) have been synthesized using soft chemical methods. Compound 1 crystallizes as light blue needles from the reaction of a mixture of CuSO4. 5H(2)O, 4,4'-bipyridine, and H2O in the mole ratio 1:1:2778, that was heated to 200 degrees C for 24 h. The structure of 1 consists of linear cationic chains of {Cu(4,4'-bpy)(H2O)(3)}(2+) with SO42- anions as spacers between the chains. Compound 2 crystallizes as dark blue rectangular plates from the reaction of a mixture of CuSO4. 5H(2)O, bpe, and H2O in the mole ratio 1:1:1111, that was initially left to stand at room temperature for 24 h and then heated to 120 degrees C for an additional 24 h. The structure of 2 exhibits rectangular grids constructed from {Cu(bpe)(2)}(2+) coordination units with linear {Cu(bpe)(H2O)(2)(SO4)(2)}(2-) chains threaded through the grids. Compound 3 crystallizes as light blue shards from the reaction mixture CuSO4. 5H(2)O, bpe, and H2O in the mole ratio 1:1:1111, that was left at room temperature for 24 h and then heated to 120 degrees C for 72 h. The structure of 3 consists of one-dimensional [Cu(bpe)(H2O)](2+) cationic chains linked together through the SO42- anions to form a three-dimensional framework. Crystal data: C10H18N2O9SCu (1): hexaganal P6(5), a = 11.2058(2) Angstrom, c = 21.5947(5) Angstrom, V = 2348.35(8) Angstrom, D-calc = 1.722 g cm(-3); structure determination based on 2255 reflections converged at R1 = 0.0488. C18H19N3O6SCu (2): monoclinic, C2/c, a = 22.9863(1) Angstrom, b = 13.4702(1) Angstrom, c = 13.4902(1) Angstrom, beta = 106.030(1)degrees, V = 4014.71(5), D-calc = 1.552 g cm(-3); 3504 reflections, R1 = 0.0396. C12H12N2O5SCu (3): monoclinic Pn, a 7.851(2) Angstrom, b = 9.9062(3) Angstrom, c = 9.1407(2) Angstrom, beta = 98.207(1)degrees, V = 652.91(3) Angstrom, D-calc = 1.850 g cm(-3); 1968 reflections, R1 = 0.0274.