Solid state coordination chemistry of copper with pyridyltetrazoles: Structural consequences of incorporation of coordinating anions

The hydrothermal reactions of various Cu(II) salts with 3- and 4-pyridinetetrazole and pyrazinetetrazole were exploited in the preparation of a series of Cu(II) and Cu(I) azolate materials. The parent copper/pyridyltetrazole compositions are observed in the two-dimensional [Cu(3-pyrtet)2] (1), the reduced three-dimensional [Cu(4-pyrtet)] (2) and reduced two-dimensional [Cu(4-pyrtet)]·0.5DMF (3·0.5DMF) (Hpyrtet = pyridyltetrazole). The consequences of introducing coordinating anions are revealed in the structures of the one-dimensional [CuCl2(4-Hpyrtet)]·0.5H2O (4·0.5H2O) and the two-dimensional [Cu2I2(4-Hpyrtet)] (5) and [Cu(acac)(4-pyrtet)] (7) (acac = acetylacetonate; H2en = ethylenediammonium cation). The pyrazinetetrazolate derivative [H2en]0.5[CuCl2(prztet)] (Hprztet = pyrazinetetrazole) (6) is one-dimensional, but structurally distinct from the chain observed for 4.

Graphical abstractHydrothermal methods were used to prepare a series of Cu(II) and Cu(I) coordination polymers with 3- and 4-pyridyltetrazole linkers. The one-dimensional structures of [CuCl2(4-Hpyrtet)] and [CuCl2(prztet)]nn− are shown (prztet = pyrazinetetrazole).Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Hydrothermal methods were used to prepare a series of copper-pyridyltetrazole coordination polymers. ► Structural consequences of variations in the position of the pyridyl nitrogen donor. ► Structural consequences of the incorporation of coordinating anions. ► Facile reduction to Cu(I) of Cu(II) starting materials yields unusual and unexpected materials.