Assembly of Heterometallic Clusters and Coordination Polymers by Combining Mo−S-Based Clusters with Mn²⁺

Addition of [MoV2O2S2(edt)2]2- (edt =1,2-ethanedithiolate) to acetonitrile and/or methanol solutions of MnII containing bipyridines [4,4‘-trimethylenedipyridine (TDP), 4,4‘-bipyridine (4,4‘-bpy), 2,2‘-bipyridine (2,2‘-bpy)] or 15-crown-5 produces three new heterometallic cluster coordination polymers, [Mn2{Mo2O2S2(edt)2}2(TDP)3(CH3OH)2(NCMe)2]·3CH3OH·0.25MeCN (1), [Mn(TDP)2(H2O)2]2+[Mn{Mo2O2S2(edt)2)2(TDP)2}]2-·6CH3OH (2), [Mn{Mo2O2S2(edt)2}(TDP)2(CH3OH)(H2O)]·CH3OH (3), and three new multinuclear clusters, [Mn{Mo2O2S2(edt)2}(4,4‘-bpy)(CH3OH)4]·0.5(4,4‘-bpy) (4), [Mn{Mo2O2S2(edt)2}(2,2‘-bpy)2]·2CH3OH (5), and (NEt4)2[Mn(15-crown-5){Mo2O2S2(edt)2}2] (6). All compounds were characterized by X-ray crystallography. The coordination mode of Mn in these compounds depends on the ligands and the crystallization conditions. Compound 2 readily converts to 1 or 3 depending on the reaction and solvent conditions. Compounds 1 and 2 were analyzed using thermogravimetric analysis combined with mass spectroscopy (TG-MS) in the temperature range 25−500 °C. The room-temperature magnetic moments for compounds 1−6 were determined.