STRUCTURE OF MACROCYCLE CONTAINING AZO AND AZOXY UNITS AND THEIR COMPLEXES. Yu.A.Simonov, Institute of Applied Physics, 2028 Kishinev, Moldova and J.Biernat and E.Luboch, Technical University of Gdansk, 80-952 Gdansk, Poland

Compounds containing the azo or azoxy units find application in the chemical sensors and the original materials for Langmuir films. A one step synthesis of both azoxy and azo crown analogues was performed by reducing bis(2-nitrophenoxy)-3-oxapentane with sodium stannite. According to X-ray analysis the 13-membered macrocycles have cis oriented phenyl residues in the azo compound (L13), whereas their orientation in the azoxy compound (L13-O) is trans. Their 16-membered analogues, ( L16) and (L16-O) have been obtained. During the macrocycles interaction with NaI and KI the following complexes were isolated and structurally characterized: [Na(L13)²]I, [Na(L13-O)2]I, [K(L16-O)2]I. From every crown ether molecule sodium atoms are coordinated by three oxygen and one nitrogen atoms placed in the antiprism corners. Na-O and Na-N distances are 2.31-2.58 and 2.50-2.59Å, respectively. In both cases phenyl residues are in trans-position in respect to the -N=N- (-N=N(O)-) bond. Potassium atom in [K(L16-O)2]I compound is ten-coordinated as a pentagonal antiprism. K-O and K-N distances are 2.83-2.92 and 3.01Å respectively. Phenyl residues have trans orientation here. In all described sandwich-like structures intramolecular stacking interaction between phenyl moieties occurs. L16-O macrocycle forms the inclusion compound with NaI with the metal : ligand stoichiometry 1:1. Sodium atom coordination polyhedron is a pentagonal pyramid. In the crystal intermolecular stacking interaction was found.