Synthesis and Structures of Dimanganese(II) Complexes with Spirotricyclic [Mn(μ‐Ge2Se7)Mn] and [Mn(μ‐Sn2Se6)Mn] Cores

Solvothermal reaction of [MnCl2(cyclam)]Cl with GeSe2at a 1:1 molar ratio in CH3OH/H2O (1/1) at 150 °C affords the dimanganese(II) complex [{Mn(cyclam)}2(μ‐Ge2Se7)]·CH3OH·1.5H2O (1) with a spirotricyclic [Mn(μ‐Ge2Se7)Mn] core. The strained four‐membered Mn‐Set‐Ge‐Set′ rings (Set= terminal Se atom) exhibit long Mn‐Setdistances in the range 2.725(2)–2.745(2) Å and narrow average Set‐Mn‐Set′ angles of 85.87(4)°. The solvothermal reaction of [MnCl2(cyclam)]Cl with SnSe and Se leads to formation of the analogous complex [{Mn(cyclam)}2(μ‐Sn2Se6.15)] (2), in which bridging [Sn2Se6]4−and [Sn2Se7]4−ligands are disordered at a ratio of 85:15. Employment of [MnCl2(terpy)] under similar conditions generates two complexes of the formula [{Mn(terpy)}2(μ‐Sn2Se6)] 3and 4, of which the former also contains a spirotricyclic core, whereas the Setatoms of the latter coordinate symmetry‐related MnIIatoms in a 1‐D polymer. The Mn‐Setbond distances of 2.584(1) and 2.549(1) Å in the resulting chair‐shaped eight‐membered rings of 4are much shorter than in 1and 2.