Hydrothermal synthesis and structures of materials of the M(II)/tetrazole/sulfate family (M(II) = Co, Ni; tetrazole=3-and 4-pyridyltetrazole and pyrazinetetrazole)

Hydrothermal reactions of cobalt or nickel sulfate with the appropriate substituted tetrazole yielded a series of compounds of the M(II)/tetrazolate/sulfate family. While the parent compound [Co(prztet)(2) (H2O)(2)]center dot 0.5H(2)O (1.0.5H(2)O; prztet = pyrazinetetrazolate) is molecular, the remaining materials exhibit extended structures. Thus, [Co-2(4-pyrtet)(SO4)(OH)(H2O)]center dot 1.5H(2)O (2.1.5H(2)O), [Co3F2(SO4)(3-pyrtet)(2) (H2O)(4)] (4) and [Ni3F2(SO4)(3-pyrtet)(2)(H2O)(4)] (5) are two-dimensional, in contrast to [Co-4(prztet)(6) (SO4)(H2O)(2)] (3) and [Ni-5(3-Pyrtet)(4)(SO4)(2)(OH)(2)(H2O)(2)]center dot 0.5H(2)O (6.0.5H(2)O) which are three-dimensional (3-pyrtet = 3-pyridinetetrazolate; 4-pyrtet = 4-pyridinetetrazolate). The sulfate-containing phases exhibit a variety of cluster-based secondary building units: variants of the common trinuclear motifs in 2, 4 and 5, a tetranuclear cluster core in 3, and a pentanuclear building block in 6. The sulfate ligands adopt monodentate and mu(2)-, mu(3)- and mu(4)-bridging modes in the structures. (C) 2012 Elsevier Ltd. All rights reserved.