Anion Tuning of Cu(II)/4,4'-Bi-1,2,4-Triazole Coordination Polymers

Nine Cu-II coordination compounds based on 4,4'-bi-1,2,4-triazole (btr), [Cu-2(N-btr)(2)(OAc)(4)]center dot 4H(2)O (1), [Cu(NI,NI'-btr)(2)-(H2O)2][CdBr4(H2O)]center dot 3H(2)O (2), [Cu(NI,NI'-btr)(2)(H2O)(2)]S2O6 center dot 4H(2)O (3), [Cu(NI,NI'-btr)(2)(H2O)(2)](NO3)(2)center dot 2H(2)O (4), [Cu-2(NI,NI'-btr)(2)(mu(3)- btr)(2)(NO3)(2)](NO3)(2)center dot 2H(2)O (5), [Cu(NI,NI'-btr)(2)(DMF)(2)](NO3)(2)center dot 2C(2)H(5)OH (6), [Cu(NI,NI'-btr)(3)](CF3CO2)(2) (7), [Cu(NI,NI'-btr)(2)(N-btr)(2)](CCl3CO2)(2)center dot 5H(2)O (8) [Cu-3(mu(2)-OH)(2)(mu(4)-btr)(mu(3)-btr)(2)(NI,NI'-btr) (H2O)(CF3CO2)] (CF3CO2)(3)center dot 4H(2)O (9), were synthesized by reaction of btr with the corresponding Cu-III salts in aqueous or DMF/ethanol solution and their structures were established with single X-ray diffraction. The coordination behavior of btr, which changes from simple monodentate, to NI,NI'-bi-, tri- and tetradentate binding modes, and the influence of the counteranions lead to a structural variety of the coordination compounds, ranging from molecular Chinese lanterns of type 1, through 2D square grids (2-4, 6, 8) and 3D octahedral networks (7), to 3D eight-connected frameworks (5, 9) that based on the dinuclear [Cu-2(trz)(2)](4+) and linear trinuclear [Cu-3(mu(2)-OH)(2)(H2O)(2)](4+) units as nodes.