Two-dimensional coordination polymer formed due to the unusual coordination of C=O group in bis-dioxolene manganese complex

Ditopic ligand - 4,7-di(tert-butyl)-5,6-dihydro-1,3-benzodithiole-2,5,6-trione (o-quinone having fused 1,3-dithiolene-2-one cycle (-S-(C = O)-S-) in back position) interacts with Mn-2(CO)(10) in toluene forming 2D-coordination polymer which layers are subdivided by the solvent molecules. Each manganese atom has six coordination environment which consists of square planar bis-dioxolene fragment and additional axial coordination is provided by two oxygen atoms of C = O group of -S-(C = O)-S- five-membered cycle from adjacent bis-dioxolene manganese fragment. Four bis-dioxolene manganese fragments form cycle which is the unit cell of 2D-polymer. Weak coordination of C = O group with manganese atom can be simply destroyed. Re-crystallization of complex from tetrahydrofuran leads to the decomposition of the 2D structure and results in octahedral mononuclear (THF)(2)Mn(semiquinone)(catecholate) complex.