Heterobimetallic compounds [L-1,OVV=O -> Fe(metsalophen)(H2O)] (1) and [(LOVV)-O-2=O -> Fe-(metsalophen)(H2O)]CH3CN (2), where H2L1 and H2L2 are tridentate dithiocarbazate-based Schiff base ligands, containing a discrete V-V-mu-O-Fe-II angular core have been synthesized for the first time through a targeted synthesis route: confirmation in favor of such a heterobimetallic core structure has come from single-crystal X-ray diffraction analysis and electrospray ionization mass spectrometry.