5-Hydroxy-1,3-diketonate ligands have been found to stabilize dimeric complexes and tetrameric lanthanoid clusters dependent on the degree of steric bulk provided by the presence or absence of a methoxy group. Treatment of (R/S,Z)-1'-hydroxy-3-(hydroxy(phenyl)methylene)bi(cyclopentan)-2-one (Hhpb) and the p-methoxyphenyl derivative (Hhmb) with [LnCl(2)(H(2)O)(6)]Cl yields clusters of composition [Ln(4)(Cl)(2)(O)(hpb)(6)]Cl(2) (Ln = Nd (1), Ho (2), Tb (3), and Er (4)) and [Ln(2)(hmb)(5)]Cl (Ln = La (5), Nd (6), Tb (7), Dy (8), and Er (9)). Single crystal X-ray analysis of the tetranuclear cluster has revealed the lanthanoid core to be in a tetrahedral arrangement around a central mu(4)-oxygen, bridged by symmetrical chlorides and shrouded in six bridging hpb ligands. The dimeric complexes are stabilized by three bridging and two terminal hmb ligands. In each instance, double or single cationic charges respectively are balanced by chloride anions.