The complex [Mn2(BPMAPS)(μ-OAc)2(hemi)]PF6 (1), where hemi is the hemiacetal group, methoxy(2-pyridyl)methoxo, was prepared from bis[3-(2-pyridylmethyleneamino)phenyl] sulfone (BPMAPS), 2-pyridinecarbaldehyde, and manganese(II) acetate in methanol. The complexes Mn2(BPMAPS)(μ-OAc)2(μ-1,1-OAc)(η1-OAc) (2) and Co2(BPMAPS)(μ-OAc)2-[μ-(η2:η1)OAc](η1-OAc) (3) were prepared from manganese(II) acetate and cobalt(II) acetate, respectively, with BPMAPS in methanol. All three complexes were characterized by elemental analysis, FT-IR, MS, UV–Vis spectroscopy, and X-ray crystallography. The manganese ions of complex 1 are bridged by a hemiacetal through the oxygen atom of the alkoxo with the nitrogen atom of the pyridine group coordinating to one of the manganese atoms. The metal ions of complexes 2 and 3 are bridged by acetato groups in μ-1,1 or μ-η2:η1 modes, respectively.