Abstract: | A series of self‐assembled “double saddle”‐type trinuclear complexes of [Pd3L′3 L 2] formulation have been synthesized by complexation of a series of cis‐protected palladium(II) components with a slightly divergent “E‐shaped” non‐chelating tridentate ligand, 1,1′‐(pyridine‐3,5‐diyl)bis(3‐(pyridin‐3‐yl)urea ( L ). The cis‐protecting agents L′ employed in the study are ethylenediamine (en), tetramethylethylenediamine (tmeda), 2,2′‐bipyridine (bpy), and 1,10‐phenanthroline (phen), for 1 , 2 , 3 , and 4 , respectively. The crystal structures of [Pd3(tmeda)3( L )2](NO3)6 ( 2 ), [Pd3(bpy)3( L )2](NO3)6 ( 3 ), and [Pd3(phen)3( L )2](NO3)6 ( 4 ) unequivocally support the new architecture. Two of the “double saddle”‐type complexes ( 3 and 4 ) are suitably crafted with π surfaces at the strategically located cis‐protecting sites to facilitate intermolecular π–π interactions in the solid state. As a consequence, six units of the 3 (or 4 ) are assembled, by means of six‐pairs of π–π stacking interactions, in a circular geometry to form an octadecanuclear molecular ring of [(Pd3L′3 L 2)6] composition. The overall arrangement of the rings in the crystal packing is equated with the traditional Indian art form rangoli. |