Two novel polynuclear complexes {NaFe₄(μ₄-O)(L)₄(μ₂-Cl)[Fe(CN)₅NO](H₂O)(DMF)₂} (1) and {NaFe₄(μ₄-O)(L)₄(μ₂-OEt)[Fe(CN)₅NO](H₂O)(DMF)₂} (2) have been prepared using the tetradentate N-(2-hydroxy- ethyl)-3-methoxysalicylaldimine Schiff-base ligand (H₂L) with the help of [Fe(CN)₅NO]^2- linkers, where the ligand was in situ synthesized through the condensation of o-vanillin and ethanolamine in the formation process of complexes. The resulting complexes possess “boat-like” structure constructed through three Fe ions and one Na ion with the fourth Fe ion acting as the “paddle”. The “hull bottom” contains an eight-membered metallamacrocycle with metalla- crown-like motif and [-M-O-] repeat unit. Both complexes display three-dimensional frameworks through C–H∙∙∙N hydrogen bonds, C–H∙∙∙Cl hydrogen bonds, and π-π stacking interactions with the introduction of solvent molecules and coordination anions. Variable-temperature magnetic susceptibility measurements reveal strong antiferromagnetic couplings between the metal centers in complexes 1 and 2.