Abstract
The hydro/solvothermal reactions of Cu(I)/Cu(II) salt, NaN(3), and acetonitrile in water or methanol yield two noninterpenetrated supramolecular networks containing 1D hexagonal and square nanochannels, {[Cu(Mtta)]x0.17H(2)O}(n )(1) and its pseudopolymorph [Cu(Mtta)](n) (2) (Mtta = 5-methyl tetrazolate), involving ligand in-situ formation by cycloaddition of nitriles and azides. The copper(I) centers in both complexes are all bridged by Mtta ligands, forming the different shapes of the cavity. (1) exhibits an unprecedented uniform (8, 3) topological metal network, whereas (2) is a 3-connected (8(2)10) metal net.

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