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)(SO 4)]·2H2O, [Cu(bpe)2][Cu(bpe)(H2O)2(SO4) 2]·2H2O

Douglas Hagrman, Robert P. Hammond, Robert Haushalter, Jon Zubieta

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Abstract

Three new members of the copper sulfate/heterocyclic diamine family [Cu(4,4′-bpy)(H2O)3-(SO4)]·2H 2O (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 SO42- 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 SO42- 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, Dcalc = 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), Dcalc = 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, Dcalc = 1.850 g cm-3; 1968 reflections, R1 = 0.0274.

Original languageEnglish (US)
Pages (from-to)2091-2100
Number of pages10
JournalChemistry of Materials
Volume10
Issue number8
StatePublished - Aug 1 1998

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ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

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