Syntheses and structures of metal tetrazole coordination polymers

Two salts and seven copper(i/ii) and silver(i) coordination polymers containing tetrazolyl ligands have been hydro(solvo)thermal synthesized by metal salts, NaN3 and various nitriles generated via [2 + 3] cycloaddition reactions of organonitriles and sodium azide. The study also shows that in some cases the azide can play a dual role in the in situ syntheses of metal tetrazole complexes, namely, starting material for tetrazole ligand and co-ligand in the tetrazole-based coordination complexes. Compounds 1 and 2 are simple salts of ammonium and sodium 5-methyltetrazolate. Compound 3 has a 3-D framework with intersecting channel and unprecedented (49.6 6) topology constructed from mixed-valent Cu8 clusters. Compounds 4 and 5 are isomorphous, and have 3-D organic-inorganic frameworks constructed by [M2(mtta)]+ (Hmtta = 5-methyltetrazole) ribbon and [M2(N3)]+ (M = Cu, Ag) layer two types of structural motifs, which contains an 4-1,1,1,3 azide. Compound 6 is a 3-D four-connected chiral complex with (42.8 4)Cu(42.82.102) tta topology. The structure of 7 consists of 2-D three-connected layers that are linked by ligand-unsupported Ag(i)⋯Ag(i) interactions to form a 3-D supramolecular array. Compound 8 shows a 3-D chiral framework containing tetrahedrally and linearly coordinated Ag(i) ions and 3- and 4-two types of 5-propyltetrazolate. Compound 9 has a 2-D layered structure formed by linkage of [Ag(tetrazolyl)] ribbons via C-C and N-Ag bonds. Magnetic measurement confirmed that there are two Cu(ii) ions and six Cu(i) ions per Cu8 unit consistent with a mixed-valent Cu(i,ii) complex.