The polydentate ligand 2,6-bis(5-(2-hydroxyphenyl)-pyrazol-3-yl)-pyridine, H4L, exhibits a series of coordination pockets favoring the establishment of metal sequences with predetermined motifs, together with a degree of flexibility for the formation of clusters with various overall topologies. With Cu(II) under strong basic conditions it has a marked tendency to stabilize a cyclic [Cu16L8] cluster. The sequential formation of this compound via [Cu7L8](2-) intermediates, recognized in its structure, is suggested by crystallographic evidence, which shows the persistent formation of the complex salt (NBu4)(2)[Cu7L8] in the presence of the organic cation. Also, the crystallographic identification of the related cluster [Cu11L5(OH)(2)(py)(12)] from similar reaction conditions underscores from this simple reaction system. the rich multiplicity of species attainable