Synthesis, characterization and crystal structures of Cu(II) and Pd(II) complexes of the pentadentate mixed donor macrocycle, [17]aneNO2S2

An aza-oxa-thia macrocycle, 5,14-dioxa-2,17-dithia6](1,2)benzeno6](2,6)pyridinophane, L1, the related smaller macrocycle 2,14-dithia-11-oxa-3](1,2)benzeno6](2,6)pyridinophane, L2, and the complexes with Pd(II) and Cu(II) of the macrocycle, L1, have been synthesized. The crystal structure of L2 and those of the two metal complexes have been determined. In the complexes, the metal ions adopt exclusively square planar geometry in which the pyridine nitrogen, two sulfurs and one chlorine atom are coordinated and there is no appreciable interaction with the oxygen donors. Thus, the `hard-soft acid-base' principle is illustrated by the behaviour of L1. The structures of both complexes are compared with the previously reported mixed aza-thia macrocycle, 2,5,14,17-tetrathia6](1,2)benzeno6](2,6)pyridinophane. The crystal structure of the smaller macrocycle, L2, is also discussed and due to the nature of its smaller cavity, attempts to make complexes with it have not been successful.