Polydentate ligands 2-[(2-hydroxypropylimino)methyl] phenol (L) and pyridine-2,6-dicarboxylic acid (H2pda) have been used in the synthesis of binuclear transition metal complexes. A new doubly end-on azido-bridged binuclear nickel(II) complex with formula [ (µ1,1-N3)2(L)2(N3)2] · H2O (1) and a bis-µ-hydroxo-bridged dinuclear chromium(III) complex with the formula [ (OH)2(pda)2(H2O)2] (2) have been synthesized and characterized by single crystal X-ray diffraction and magnetic studies. Compound 1 displays intramolecular intermetallic ferromagnetic coupling with J = 28.32 cm−1 and D = −19.30 cm−1 based on the Hamiltonian Ĥ = −2JŜ 1 Ŝ 2 − D( + ) − gβH(Ŝ 1 + Ŝ 2). Compound 2 displays intramolecular intermetallic antiferromagnetic coupling with J = −6.56 cm−1 based on the Hamiltonian Ĥ = −2JŜ 1 Ŝ 2 − j(Ŝ 1 Ŝ 2)2.