The use of phenyl-2-pyridyl ketone oxime and di-2-pyridyl ketone oxime in Mn chemistry has led to hexanuclear clusters with unprecedented (Mn(II)(4)Mn(III)Mn(IV)) or extremely rare (Mn(II)Mn(III)(5) and Mn(II)(3)Mn(III)(3)) metal oxidation-state combinations and uncommon structural motifs.