COORDINATION CHEMISTRY OF THIOETHER PYRIDAZINE MACROCYCLES .2. SYNTHESIS, STRUCTURAL AND SPECTROSCOPIC STUDIES OF DINUCLEAR COPPER(II) AND POLYNUCLEAR COPPER(I) AND SILVER(I) COMPLEXES OF A TETRATHIAPYRIDAZINOPHANE MACROCYCLIC LIGAND

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 (1) and [CuL3Br2]2 (11) 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 P1BAR, with a = 9.410(2) angstrom, b = 10.291(2) angstrom, c = 9.208(2) angstrom, alpha = 108.56(1)-degrees, beta = 91.82(2)-degrees, gamma = 68.04(1)-degrees, V = 780.1(2) angstrom3, and Z = 2(R = 0.035, R(w) = 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 P2(1)/n, with a = 9.382(4) angstrom, b = 19.274(4) angstrom, c = 10. 190(3) angstrom, beta = 106.35(3)-degrees, V = 1768(1) angstrom3, and Z = 4 (R = 0.036, R(w) = 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.