Motivated by the precedence for catalysts comprising Cr(III) in CX2/epoxide ROCOP (X = O, S), a series of heterobimetallic Cr(III)AM (AM = Li, Na, K, Rb, Cs) complexes was targeted based on the heterobinucleating ligand H2L (ESI Section S2). Treatment of H2L with Cr(OAc)2 following aerobic oxidation in presence of HOAc yields LCr which can be easily coordinated to the alkali metal acetates by reaction with AMOAc (AM = Li, Na, K, Rb, Cs) forming LCr AM which were characterized using single crystal XRD, HR-ESIMS, UV-VIS and elemental analysis. As shown in Figure the complexes form dimeric arrangements in the solid state with different bridging modes depending on the alkali metal. However all complexes feature six-coordinate chromate centres through equatorial coordination of the N,N,O,O donors and axial coordination through two acetate oxygens. Also, LCr Na/K/Cs show donor solvent coordination at the alkali metal. LCr Na , LCr K and LCr Rb exhibit alkali-metal coordination via all four half-crown donor oxygens of one ligand scaffold. In LCr on the other hand Li coordination occurs via one phenolate and one methoxy oxygen centre from two different ligand scaffolds. LCr Cs forms a doubledecker type arrangement in which one Cs is sandwiched between two half-crown units while another Cs face caps one side of the dimer.