Abstract: | In the title complex, [Mn(C5H4NO)2(C5H5NO)2]n or [Mn(μ‐3‐PyO)2(3‐PyOH)2]n (3‐PyO− is the pyridin‐3‐olate anion and 3‐PyOH is pyridin‐3‐ol), the MnII atom lies on an inversion centre and has octahedral geometry, defined by two N atoms and two deprotonated exocyclic O atoms of symmetry‐related pyridin‐3‐olate ligands [Mn—N = 2.3559 (14) Å and Mn—O = 2.1703 (11) Å], as well as two N atoms of terminal 3‐PyOH ligands [Mn—N = 2.3482 (13) Å]. The MnII atoms are bridged by the deprotonated pyridin‐3‐olate anion into a layer structure, generating sheets in the (01) plane. These sheets are linked by O—H⋯O hydrogen bonds. There are also π–π and C—H⋯π interactions in the crystal structure. |