1,4-Di(1,2,3,4-tetrazol-2-yl)butane as a precursor of new 2D and 3D coordination polymers of Cu(II)

Abstract

A series of new coordination polymers of Cu(II) have been prepared in a reaction between copper(II) perchlorate or tetrafluoroborate salt and a novel ligand 1,4-di(1,2,3,4-tetrazol-2-yl)butane (bbtz). The compounds were characterised by an elemental analysis, TG measurements, IR, EPR and UV–Vis spectroscopy. Crystal structures of bbtz and five complexes of Cu(II) were determined by a single crystal X-ray diffraction measurement performed at 100 K. The composition and architecture of the obtained complexes strongly depend on the reaction conditions especially on the kind of solvent. Investigated complexes are composed of polymeric macrocations and non-coordinated anions. In all cases the bbtz molecules act as the bidentate ligand coordinated to metal(II) ions via N4, N4 ′ nitrogen atoms from tetrazole rings. The complexes {[Cu(bbtz) 2(MeOH) 2]X 2} ∞ (X=ClO 4 −, BF 4 −) crystallise from methanol as 2D coordination polymers. In these compounds central metal ions are coplanar linked by molecules of bbtz and a coordination sphere is completed by axially coordinated solvent molecules. The complexes {[Cu(bbtz) 3]X 2} ∞ (X=ClO 4 −, BF 4 −) were synthesised in EtOH/H 2O solvent system and posses a common network topology. In this group of complexes each central atom is linked by ligand molecules to six other in plane arranged central atoms resulting in 2D networks. Reactions between Cu(II) salts and bbtz performed in absolute ethanol resulted in the formation of the next type of product. In {[Cu(bbtz) 3](ClO 4) 2·2EtOH} ∞ neighboured copper(II) ions are linked by ligand molecules in the three directions what leads to the formation of 3D net. A crystal of this complex is composed of two mutually interpenetrated 3D networks.