Methanolothermal Syntheses, Crystal Structures and Optical Properties of Binuclear Transition Metal Complexes Involving the Bidentate S-Donor Ligand μ-Sn2S6

New binuclear transition metal complexes concerning the bidentate S-donor ligand mu-Sn2S6, [{Mn(tren)}(2)(mu-Sn2S6)] (1), [{Zn(tren)}(2)(mu-Sn2S6)] (2), and [{Mn(tepa)}(2)(mu-Sn2S6)] (3) [tren = tris(2-aminoethyl) amine, tepa = tetraethylenepentamine] were prepared under methanolothermal conditions. The Mn2+ and Zn2+ ions are coordinated by a tren ligand, forming [TM(tren)](2+) (TM = Mn, Zn) units. As a bidentate bridging ligand, the hexathiobistannate [Sn2S6](4-) anion joins two [TM(tren)](2+) units via trans terminal S atoms to form neutral complexes 1 and 2. Both Mn2+ and Zn2+ ions are in a trigonal bipyramidal environment. In 3, the Mn2+ ion binds a pentadentate tepa ligand to give a [Mn(tepa)](2+) unit. Two [Mn(tepa)](2+) units are connected by a mu-Sn2S6 bridging ligand, forming neutral complex [{Mn(tepa)}(2)(mu-Sn2S6)], in which the Mn2+ ion is in an octahedral environment. Intermolecular N-H center dot center dot center dot S H-bonding interactions connect 1-3 into layered structures, while 3 forms a three-dimensional network via the N-H center dot center dot center dot S H-bonds. 1-3 exhibit possible semiconducting properties with the band gaps at 2.3, 2.7 and 2.4 eV, respectively. Graphical Abstract Transition metal complexes concerning the bidentate S-donor ligand mu-Sn2S6, [{Mn(tren)}(2) (mu-Sn2S6)], [{Zn(tren)}(2)(mu-Sn2S6)], and [{Mn(tepa)}(2) (l-Sn2S6)] were respectively synthesized using tris(2-aminoethyl) amine (tren) and tetraethylenepentamine (tepa) as second ligands under mild methanolothermal conditions. [GRAPHICS] .