Coordination chemistry of thioether–pyridazine macrocycles II. Synthesis, structural and spectroscopic studies of dinuclear copper(II) and polynuclear copper(I) and silver(I) complexes of a tetrathiapyridazinophane macrocyclic ligand

Abstract

The preparation and properties of the thioether–pyridazine macrocycle (L3; C11H16N2S4) containing one pyridazine subunit, and its copper(II), copper(I), and silver(I) complexes are described. Magnetic susceptibility data (5–300 K) for the binuclear complexes [CuL3Cl2]2 (I) and [CuL3Br2]2 (II) have been fitted to the Friedberg magnetization expression with a molecular field correction. Intradimer antiferromagnetic exchange is weak (−2J < 18 cm−1), with even weaker interdimer exchange (−zJ′ < 0.3 cm−1). The complexes [CuL3Cl]x (III) and [AgL3ClO4]x (V) have been characterized by X-ray crystallography. III crystallizes in the triclinic system, space group [Formula: see text], with a = 9.410(2) Å, b = 10.291(2) Å, c = 9.208(2) Å, α = 108.56(1)°, β = 91.82(2)°, γ = 68.04(1)°, V = 780.1(2) Å3, and Z = 2(R = 0.035, Rw = 0.031 for 1856 reflections). The ligand acts as a bidentate, S2, bridge between dinuclear Cu2Cl2 units in a double stranded polymer. III crystallized in the monoclinic system, space group P21/n, with a = 9.382(4) Å, b = 19.274(4) Å, c = 10.190(3) Å, β = 106.35(3)°, V = 1768(1) Å3, and Z = 4 (R = 0.036, Rw = 0.029 for 1776 reflections). The structure consists of a polymeric, two dimensional sheet structure, involving pseudo-tetrahedral silver ions linked by exo-bidentate, S2, ligands and bidentate perchlorates.