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Three-Dimensional Organic/Inorganic Hybrid Materials Constructed from One-Dimensional Copper Diamine Coordination Polymers Linked by Bridging Oxoanion Tetrahedra:  [Cu(dpe)(MoO4)] and [Cu(dpe)(SO4)(H2O)] (dpe = 1,2-trans-(4-pyridyl)ethene)

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journal contribution
posted on 19.01.1998, 00:00 by Douglas Hagrman, Robert C. Haushalter, Jon Zubieta
The hydrothermal reaction of CuSO4·5H2O, dpe, MoO3, and water in the mole ratio 1:2:2:900 at 120 °C for 111 h yielded [Cu(dpe)(MoO4)] (1). Upon omitting the molybdate component, the reaction of CuSO4·5H2O, dpe and water in the mole ratio 1:1:1111 at 120 °C for 72 h yielded [Cu(dpe)(SO4)(H2O)] (2). The structure of 1 is constructed from {Cu(dpe)}2+ linear chains bridged through {MoO4}2- tetrahedra into a three-dimensional framework, while that of 2 consists of {Cu(dpe)}2+ chains bridged through {SO4}2- tetrahedra. However, while the {MoO4}2- units of 1 adopt the η3-coordination mode, each linking three adjacent chains, the {SO4}2- units of 2 assume η2-coordination and bridge only two neighboring chains. These differences in {EO4}2- coordination modes are reflected in the dramatically different three-dimensional structures displayed by 1 and 2. Crystal data:  C12H10CuMoN2O4 (1), orthorhombic Pbcn, a = 22.0462(1) Å, b = 12.2957(2) Å, c = 9.7560(2) Å, V = 2644.59(7) Å, Z = 8, Dcalc = 2.038 g cm-3; 3202 reflections, R1 = 0.056. C12H12CuN2O5S (2), monoclinic Pn, a = 7.2851(2) Å, b = 9.9062(3) Å, c = 9.1407(2) Å, β = 98.207(1)°, V = 652.91(3) Å, Z = 2, Dcalc = 1.830 g cm-3; 1968 reflections, R1 = 0.027.

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