3D Coordination Framework with Uncommon Two-Fold Interpenetrated {3(3).5(9).6(3)}-lcy Net and Coordinated Anion Exchange

Reaction of tetrazole-1-acetic acid with CuSO4 center dot 5H(2)O produces two novel 3D coordination frameworks: ([Cu-3(mu(3)-OH)(eta(1):eta(1):eta(1):mu(3)-SO4)-(tza)(3)]center dot 3CH(3)OH center dot H3O)(n) (1: Htza=tetrazole-1-acetic acid) and {[Cu-4(mu(2)-OH)-(eta(2):eta(2):mu(4)-SO4)(tta)(5)]center dot 3H(2)O}(n) (2; Htta = tetrazole). Framework 1 is constructed from a trinuclear copper culster [Cu-3-(mu(3)-CH)(eta(1):eta(1):eta(1):mu(3)-SO4)] and displays a six-connected framework with uncommon {3(3).5(9).6(3)}-lcy topology. Framework 2 presents a complicated five-nodal (3,4,6)-connected net with (4(2).6)-(3.4(2).5(2).7)(4(3).6(2).8)(3(2).4(8).5(3).6(2))(4(6).8(6).10(3)) topology. The eta(2):eta(2):mu(4)-SO4 bridging mode in 2 has not been found in the reported coordination polymers. The co-ordinated SO42- anions in 1 call be replaced completely when the solid polymer is treated with an aqueous methanolic solution containing Cl anions. Detailed atomic force microscopy studies indicate a solvent-mediated rather than a solid-state mechanism for the exchange process.