Closely related macrocyclic and acyclic tridentate, pyridine derivatives, containing sulphur, and their complexes. Crystal structures of {dichloro-3,10-dithia-16-azabicyclo[l0.3.1]hexadeca-1(16),12,14-triene}copper(II) and [2,6-bis(ethyithiomethyl)pyridine]dichlorocopper(II)

Abstract

Four closely related, tridentate, pyridine derivatives, containing sulphur, three of them macrocyclic, 3,10-dithia-16-azabicyclo[10.3.1]hexadeca-1 (16),12,14-triene (L¹), 3,8- dithia-14-azabicyclo-[8.3.1]tetradeca-1 (14),10,12-triene (L²), 3,7-dithia-13- azabicyclo[7.3.1]trideca-1 (13),9,11 -triene(L³), and one acyclic, 2,6-bis(ethylthiomethyl)pyridine (L⁴), have been prepared. All contain the same co-ordination elements (NS₂) structurally placed in the same fashion, sulphur–methylene–pyridine–methylene–sulphur. Copper complexes of all the ligands and the palladium complex of L¹ have also been prepared. The molecular structures of the complexes [CuL¹Cl₂] and [CuL⁴Cl₂] are described. The latter is monoclinic, space group I2/c, with a= 14.669(6), b= 7.418(4), c= 29.412(8)Å, β= 103.03(4)°, and Z= 8. The former is monoclinic, space group P2/a with a= 14.677(9), b= 7.555(1), c= 29.969(4)Å, β= 101.00(2)°, and Z= 8. The different reactivity of the macrocycle ligand L¹ with respect to that of L⁴ is discussed.