Copper(II) and zinc(II) complexes with macrocyclic ligand: Structure variation via counteranion and co-ligand

Seven new metal complexes [Zn-2(L)Br-2](ClO4)(2) (1), [Cu-2(L)Er-2]Br-2 center dot 2H(2)O (2), [Cu-2(L)(H2O)(2)]-(ClO4)(4)center dot 1.03H(2)O (3), [Cu-6(L)(3)(H2O)(2)Br-2(N-3)](ClO4)(9)center dot 2H(2)O (4), [Cu-4(L)(2)Br-4(im)(2)]Br-2 center dot 15H(2)O (5), [Cu-2(L)(bpy)(2)](ClO4)(4)center dot 2bpy center dot 2H(2)O (6) and [Cu-2(L)(tp)]Br-2 center dot 6H(2)O (7) (N-3(-) = azide anion; im(-) = imdazolate anion; bpy = 4,4'-bipyridine; tp(2-) = terephthalate dianion) have been synthesized by reactions of macrocyclic ligand 3,6,9,12,20,23,26,29-octaazatricyclo[29.3.1.1(14.18)]hexatriaconta-1(34),14,16,18(36),31 (35),32-hexaene (L) and metal salts with different counteranion and/or co-ligand. Interestingly, there are [Zn2L](4+)/[Cu2L](4+) dinuclear units with different conformations of chair-type in 1, 2, 6 and 7, boat-type in 5 and mixed chair- and boat-types in 3, 4. The complexes 1, 2, 3 and 6 have dinuclear molecular structure, and 4 has dimer of [Cu2L](4+) linked by azide and 5 displays tetranuclear molecular rectangle bridged by imidazolate groups, while 7 has ID chain structure in which the [Cu2L](4+) units linked by terephthalate anions. The results revealed that the structure, coordination ability and coordination mode of anions and/or co-ligands have great impact on the structure of the complexes. (C) 2010 Elsevier B.V. All rights reserved.