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 = <i>trans-</i>1,2-Bis(4-pyridyl)ethylene)

Abstract

Three new members of the copper sulfate/heterocyclic diamine family [Cu(4,4‘-bpy)(H 2 O) 3 (SO 4 )]·2H 2 O ( 1; 4,4‘-bpy = 4,4‘-bipyridine), [Cu(bpe) 2 ][Cu(bpe)(H 2 O) 2 (SO 4 ) 2 ]·2H 2 O ( 2; bpe = trans -1,2-bis(4-pyridyl)ethylene), and [Cu(bpe)(H 2 O)(SO 4 )] ( 3 ) have been synthesized using soft chemical methods. Compound 1 crystallizes as light blue needles from the reaction of a mixture of CuSO 4 ·5H 2 O, 4,4‘-bipyridine, and H 2 O 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)(H 2 O) 3 } 2+ with SO 4 2 - anions as spacers between the chains. Compound 2 crystallizes as dark blue rectangular plates from the reaction of a mixture of CuSO 4 ·5H 2 O, bpe, and H 2 O 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)(H 2 O) 2 (SO 4 ) 2 } 2 - chains threaded through the grids. Compound 3 crystallizes as light blue shards from the reaction mixture CuSO 4 ·5H 2 O, bpe, and H 2 O 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)(H 2 O)] 2+ cationic chains linked together through the SO 4 2 - anions to form a three-dimensional framework. Crystal data: C 10 H 18 N 2 O 9 SCu (1): hexaganal P 6 5, 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. C 18 H 19 N 3 O 6 SCu (2): monoclinic, C 2/ 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. C 12 H 12 N 2 O 5 SCu (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.