Preparation of Acentric Porous Coordination Frameworks from an Interpenetrated Diamondoid Array through Anion-Exchange Procedures: Crystal Structures and Properties

The formation, crystal structures, and properties of a series of three-dimensional (3-D) Cu(II) coordination polymers, [[Cu(L)2(H2O)2](PF6)2(H2O)(1.25)]n (1), [[CuL(N3)2](H2O)(1.5)]n (2), and [[CuL(H2O)(SO4)](H2O)2]n (3), with an angular bridging ligand 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (L) are reported. Complex 1 crystallizes in the tetragonal I4(1)/a space group (a = b = 13.462(2) A, c = 46.47(1) A, Z = 8), complex 2 in the orthorhombic Pna2(1) space group (a = 6.379(2) A, b = 10.060(3) A, c = 27.232(9) A, Z = 4), and complex 3 in the orthorhombic P2(1)2(1)2(1) space group (a = 5.510(2) A, b = 10.576(4) A, c = 28.34(1) A, Z = 4). Different polymeric frameworks are obtained by only varying the counterions. These include the 2-fold interpenetrated diamondoid structure of 1, the acentric alpha-Po network of 2, and the chiral open framework of 3 with (6(3)).(6(9).8) topology. The interesting anion-exchange, porous, and magnetic properties of these coordination supramolecules have been investigated in detail.