Organic/Inorganic Composite Materials:  Hydrothermal Syntheses and Structures of the One-, Two-, and Three-Dimensional Copper(II) Sulfate−Organodiamine Phases [Cu(H2O)3(4,4‘-bipyridine)(SO4)]·2H2O, [Cu(bpe)2][Cu(bpe)(H2O)2(SO4)2]·2H2O, and [Cu(bpe)(H2O)(SO4)] (bpe = trans-1,2-Bis(4-pyridyl)ethylene)

Three new members of the copper sulfate/heterocyclic diamine family [Cu(4,4‘-bpy)(H2O)3(SO4)]·2H2O (1; 4,4‘-bpy = 4,4‘-bipyridine), [Cu(bpe)2][Cu(bpe)(H2O)2(SO4)2]·2H2O (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 CuSO4·5H2O, 4,4‘-bipyridine, and H2O in the mole ratio 1:1:2778, that was heated to 200 °C for 24 h. The structure of 1 consists of linear cationic chains of {Cu(4,4‘-bpy)(H2O)3}2+ with SO4 2- anions as spacers between the chains. Compound 2 crystallizes as dark blue rectangular plates from the reaction of a mixture of CuSO4·5H2O, 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 °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 CuSO4·5H2O, bpe, and H2O in the mole ratio 1:1:1111, that was left at room temperature for 24 h and then heated to 120 °C for 72 h. The structure of 3 consists of one-dimensional [Cu(bpe)(H2O)]2+ cationic chains linked together through the SO4 2- anions to form a three-dimensional framework. Crystal data: C10H18N2O9SCu (1): hexaganal P65, a = 11.2058(2) Å, c = 21.5947(5) Å, V = 2348.35(8) Å, 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) Å, b = 13.4702(1) Å, c = 13.4902(1) Å, β = 106.030(1)°, V = 4014.71(5), D calc = 1.552 g cm-3; 3504 reflections, R1 = 0.0396. C12H12N2O5SCu (3): monoclinic Pn, a = 7.851(2) Å, b = 9.9062(3) Å, c = 9.1407(2) Å, β = 98.207(1)°, V = 652.91(3) Å, D calc = 1.850 g cm-3; 1968 reflections, R1 = 0.0274.