COMPLEXATION OF METAL-SALTS WITH MACROCYCLIC POLYETHERS IN APROTIC ORGANIC-SOLVENTS - CRYSTAL-STRUCTURES OF IONIC COMPLEXES [CUCL.15-C-5.CH3CN]2[CU2CL6] AND ([CU.15-C-5.(CH3CN)2][CU3CL8])N

Interaction of CuCl2 and CuCl2.2H2O with 15-C-5 in acetonitrile medium affords ionic complexes (CuCl.15-C-5.CH3CN)2(CU2Cl6) (I) and [(Cu.15-C-5.(CH3CN)2(CU3Cl8)]n (II) having copper in the inner cavity of the macrocycle. The copper polyhedron in the cation of I is a pentagonal bipyramid with axial chloride and acetonitrile. Copper atoms in the anion are bonded with bridging and terminal chlorides located in the apices of a strongly distorted square. The axial positions of the pentagonal bipyramid of the cation of complex II are occupied by two acetonitrile molecules. There are only bridging chlorides in the anion [CU3Cl8]2-. The polyhedron of central copper in the anion is a square bipyramidal, that of the two terminal ones is square pyramidal. Complexes I and II decompose on heating with successive liberation of acetonitrile ligand, degradation of crown ether and reduction of copper(2+) chloride into alpha-CuCl.