Syntheses, structural characterization and properties of transition metal complexes of 5,5 '-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5 ',5 ''-(1,1 '-biphenyl)-4,4 '-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5 ',5 ''-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt)

The hydrothermal chemistry of a variety of M(II) SO4 salts with the tetrazole (Ht) ligands 5,5'-(1,4-phenylene)bis(1H-tetrazole) (H(2)bdt), 5', 5 ''-(1,1'-biphenyl)4,4'-diylbis(1H-tetrazole) (H(2)dbdt) and 5,5', 5 ''-(1,3,5-phenylene)tris(1H-tetrazole) (H(3)btt) was investigated. In the case of Co(II), three phases were isolated, two of which incorporated sulfate: [Co5F2(dbdt)(4)(H2O)(6)]center dot 2H(2)O (1 center dot 2H(2)O), [Co-4(OH)(2)(SO4)(bdt)(2)(H2O)(4)] (2) and [Co-3(OH)(SO4)(btt)(H2O)(4)]center dot 3H(2)O (3 center dot 3H(2)O). The structures are three-dimensional and consist of cluster-based secondary building units: the pentanuclear {Co5F2(tetrazolate)(8)(H2O)(6)}, the tetranuclear {Co-4(OH)(2)(SO4)(2)(tetrazolate)(6)}(4-), and the trinuclear {Co-3(mu(3)-OH)(SO4)(2) (tetrazolate)(3)}(2-)for 1, 2, and 3, respectively. The Ni(II) analogue [Ni-2(H(0.67)bdt)(3)]center dot 10.5H(2)O (4 center dot 10.5H(2)O) is isomorphous with a fourth cobalt phase, the previously reported [Co-2(H(0.67)bat)(3)]center dot 20H(2)O and exhibits a {M(tetrazolate)(3/2)}(infinity) chain as the fundamental building block. The dense three-dimensional structure of [Zn(bdt)] (5) consists of {ZnN4} tetrahedra linked through bdt ligands bonding through N1, N3 donors at either tetrazolate terminus. In contrast to the hydrothermal synthesis of 1-5, the Cd(II) material (Me2NH2)(3)[Cd12Cl3(btt)(8)(DMF)(12)]center dot xDMF center dot yMeOH (DMF = dimethylformamide; x = ca. 12, y = ca. 5) was prepared in DMF/methanol. The structure is constructed from the linking of {Cd4Cl(tetrazolate)(8)(DMF)(4)}(1-) secondary building units to produce an open-framework material exhibiting 66.5% void volume. The magnetic properties of the Co(II) series are reflective of the structural building units.