A SIMPLE SYNTHETIC ROUTE TO N,N'-DIALKYL-2,11-DIAZA[3.3](2,6)-PYRIDINOPHANES - CRYSTAL-STRUCTURES OF N'-DI-TERT-BUTYL-2,11-DIAZA[3.3](2,6)PYRIDINOPHANE AND ITS COPPER(II) COMPLEX

Reaction of 2,6-bis(bromomethyl)pyridine with primary amines gave the 12-membered N,N'-dialkyl-2,11-diaza[3.3](2,6)pyridinophanes. The struc tures of N'-di-tert-butyl-2,11-diaza[3.3](2,6)pyridinophane (4) and it s copper(II) derivative [Cu(4)Cl2] (7) have been characterized by X-ra y crystal analysis. The average axial Cu-N (tertiary amine) distance o f 2.490 angstrom in 7 is appreciably longer than the related value of 2.347 angstrom in Cu(6)Cl2 . H2O.4 In 4, the two planar pyridyl rings are not in the same plane, but roughly parallel and the 12 atoms of th e macrocyclic ring constitute a syn chair-chair conformation. In compl ex 7, the copper(II) ion adopts a distorted octahedral geometry, in wh ich the tertiary amine nitrogen atoms span axial positions approximate ly normal to the square plane formed by the two pyridine nitrogens and the chloro ligands. The average Cu-N (tertiary amine), Cu-N(pyridine) and Cu-Cl distances are 2.49(2), 2.03(2) and 2.287(7) angstrom, respe ctively.