Solid-State Coordination Chemistry of Copper(II) Tetrazolates: Anion Control of Frameworks Constructed from Trinuclear Copper(II) Building Blocks

The products of the reactions of copper(II) starting materials with 4-pyridyltetrazole (4-Hpt) in N,N-dimethylformamide (DMF)/methanol solutions are determined by the anion identity and concentration. In the absence of chloride, the 3-D open-framework material [Cu3(OH)3(4-pt)3(DMF)4]·5DMF·3MeOH (1·5DMF·3MeOH) is isolated, while variations in the chloride concentration yield the 2-D and 3-D materials, 2 and 3, respectively. All three structures exhibit trinuclear copper(II) building blocks: the triangular {Cu3(μ3-OH)}5+ core in 1 and {Cu3Cl4(4-pt)4(4-Hpt)2}2− and {Cu3Cl2(4-pt)8}4− chains in 2 and 3, respectively. All three materials display microporosity, which is highly dependent on the method of sample preparation.