Assembly of heterometallic clusters and coordination polymers by combining Mo-S-based clusters with Mn2+

Addition of [(Mo2O2S2)-O-V(edt)(2)](2-) (edt) 1,2-ethanedithiolate) to acetonitrile and/ or methanol solutions of Mn-II 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, [Mn-2{Mo2O2S2(edt)(2)}(2)( TDP)(3)(CH3OH)(2)( NCMe)(2)], 3CH3OH center dot 0.25MeCN (1), [Mn(TDP)(2)(H2O)(2)](2+)[Mn{Mo2O2S2(edt)(2))(2)(TDP)(2)}](2-), 6CH(3)OH (2), [Mn{Mo2O2S2(edt)(2)}(TDP)(2)( CH3OH)(H2O)]center dot CH3OH (3), and three new multinuclear clusters, [Mn{Mo2O2S2(edt)(2)}(4,4'-bpy)(CH3OH)(4)]center dot 0.5(4,4'-bpy) (4), [Mn{Mo2O2S2(edt)(2)}(2,2'-bpy)(2)]center dot 2CH(3)OH ( 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 degrees C. The room-temperature magnetic moments for compounds 1-6 were determined.