The cobalt(II) chloride catalyzed Peterson rearrangement reactions between sulfinyldi-(pyrazolyl) and aryl(pyridyl)methanone derivatives yield di(pyrazolyl)(pyridyl)hetero-scorpionate ligands. Reaction of these ligands with Mn(CO) 5 Br in the presence of a silver salt produces the monometallic complexes {[κ 3 -PhC(pz) 2 (2-py)]Mn(CO) 3 }(O 3 SCF 3 ) (1a), {[κ 3 -PhC(pz) 2 (2-py)]Mn(CO) 3 }(PF 6 ) (1b), {[κ 3 -PhC( 4-Me pz) 2 (2-py)]Mn(CO) 3 }(PF 6 ) (2), {[κ 3 -p-BrC 6 H 4 C(pz) 2 (2-py)]Mn(CO) 3 }(PF 6 ) (3), and the bimetallic complexes [(CO) 3 Mn{m-C 6 H 4 [C(pz) 2 (2-py)] 2 }Mn(CO) 3 ](BF 4 ) 2 (5a) and {m-C 6 H 4 [C(pz) 2 (2-py)Mn(CO) 3 ] 2 }(PF 6 ) 2 (5b) (pz=pyrazolyl ring, py=pyridyl ring). These octahedral manganese complexes show interesting structural diversity, with the complexes being organized in the solid state into complex supramolecular structures by an array of non-covalent forces.