A rare all-Mn2+ decametallic cage from distorted face-sharing cubes

The preparation and crystal structure of a decametallic MnII carboxylate cluster containing neutral 2-pyridinealdoxime, (py)C(H)NOH, and its anion, (py)C(H)NO−, is reported. The reaction between Mn(O2CPh)2 · 2H2O and (py)C(H)NOH in CH2Cl2, in the presence of NH4PF6, produces the complex [Mn10(O2CPh)12{(py)C(H)CNO}6{(py)C(H)NOH}2](PF6)2 · 2.6CH2Cl2 · 1.3H2O (1 · 2.6CH2Cl2 · 1.3H2O) in good yield. The cationic complex consists of ten MnII ions assembled together by four η1:η1:η3:μ4 and two η1:η1:η2:μ3 oximato(−1) ligands, and four η1:η2:μ3View the MathML sourcePhCO2- ligands to form an unprecedented View the MathML source{MnII10(μ-OR)4(μ-OR′)2(μ3-OR′)4}10+ core, where R = PhCO and R′ = (py)C(H)N. Peripheral ligation is provided by a combination of bridging benzoates and chelating (py)C(H)NOH ligands. Dc magnetic susceptibility studies reveal the presence of dominant antiferromagnetic interactions leading to a spin ground-state of S T = 0. A survey of the ternary View the MathML sourceMnII/RCO2-/(py)C(H)NOH reaction system is attempted with comparisons to previously reported complexes.