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-<i>trans</i>-(4-pyridyl)ethene)

Abstract

The hydrothermal reaction of CuSO 4 ·5H 2 O, dpe, MoO 3, and water in the mole ratio 1:2:2:900 at 120 °C for 111 h yielded [Cu(dpe)(MoO 4 )] ( 1 ). Upon omitting the molybdate component, the reaction of CuSO 4 ·5H 2 O, dpe and water in the mole ratio 1:1:1111 at 120 °C for 72 h yielded [Cu(dpe)(SO 4 )(H 2 O)] ( 2 ). The structure of 1 is constructed from {Cu(dpe)} 2+ linear chains bridged through {MoO 4 } 2 - tetrahedra into a three-dimensional framework, while that of 2 consists of {Cu(dpe)} 2+ chains bridged through {SO 4 } 2 - tetrahedra. However, while the {MoO 4 } 2 - units of 1 adopt the η 3 -coordination mode, each linking three adjacent chains, the {SO 4 } 2 - units of 2 assume η 2 -coordination and bridge only two neighboring chains. These differences in {EO 4 } 2 - coordination modes are reflected in the dramatically different three-dimensional structures displayed by 1 and 2 . Crystal data: C 12 H 10 CuMoN 2 O 4 ( 1 ), orthorhombic Pbcn, a = 22.0462(1) Å, b = 12.2957(2) Å, c = 9.7560(2) Å, V = 2644.59(7) Å, 3 Z = 8, D calc = 2.038 g cm - 3; 3202 reflections, R 1 = 0.056. C 12 H 12 CuN 2 O 5 S ( 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, D calc = 1.830 g cm - 3; 1968 reflections, R 1 = 0.027.