Syntheses and Structures of Isoindoline Complexes of Zn(II) and Cu(II): An Unexpected Trinuclear Zn(II) Complex

Deprotonation of the tridentate isoindoline ligand 1,3-bis{2-(4-methylpyridyl)imino}-isoindoline, 4‘-MeLH, and reaction
with hydrated zinc(II) perchlorate produces an unexpected trinuclear Zn(II) complex, [Zn3(4‘-MeL)4](ClO4)2·5H2O
(1), whereas reaction with hydrated copper(II) perchlorate in methanol produces the expected mononuclear product,
[Cu(4‘-MeL)(H2O)2]ClO4 (2). X-ray diffraction shows that the trinuclear Zn(II) complex (1) contains a linear zinc
backbone, and the arrangement of ligands about the outer chiral zinc(II) atoms is helical. The two terminal zinc
ions exhibit approximate C2 site symmetry, with tetrahedral coordination by two pyrrole and two pyridyl nitrogen
atoms of the potentially tridentate isoindoline ligands. The central zinc ion exhibits approximate tetrahedral symmetry,
with coordination by four pyridyl nitrogen atoms of four different isoindoline ligands. Pyridyl−pyrrole intramolecular
π-stacking interactions contribute to the stability of the trinuclear cation. The structure of the mononuclear copper(II) complex cation in 2 is best described as a distorted trigonal bipyramid. The isoindoline anion binds Cu(II) in
both axial positions and one of the equatorial positions; water molecules occupy the other two equatorial positions.