Hexanuclear Cu3O–3Cu triazole-based units as novel core motifs for high nuclearity copper(ii) frameworks

Abstract

The asymmetric 3,5-disubstituted 1,2,4-triazole ligand H₂V (5-amino-3-picolinamido-1,2,4-triazole) by reaction with an excess of Cu(II) perchlorate (Cu : H₂V being 12 : 1) has produced a novel hexanuclear {Cu₆(μ₃-O/H)(HV/V)₃} fragment, with one triangular Cu₃(μ₃-O/H) group connected to three peripheral single Cu(II) ions through a cis–cis–trans bridging mode of the ligand, which is the building block of the three structures described here: one hexanuclear, [Cu₆(μ₃-O)(HV)₃(ClO₄)₇(H₂O)₉]·8H₂O (1), one dodecanuclear, [Cu₁₂(μ₃-O)₂(V)₆(ClO₄)₅(H₂O)₁₈](ClO₄)₃·6H₂O (2), and one tetradecanuclear 1D-polymer, {[Cu₁₄(μ₃-OH)₂(V)₆(HV)(ClO₄)₁₁(H₂O)₂₀](ClO₄)₂·14H₂O}_n (3), the last two containing hexanuclear subunits linked by perchlorato bridges. The Cu–Cu av. intra-triangle distance is 3.352(2) Å and the Cu(central)–Cu(bridged external) av. distance is 5.338(3) Å. The magnetic properties of the hexanuclear “Cu₃O–3Cu” cluster have been studied, resulting as best fit parameters: g = 2.18(1), J(intra-triangle) = −247.0(1) cm⁻¹ and j(central Cu^II – external Cu^II) = −5.15(2) cm⁻¹.