Abstract: | Reaction of MnSO4 · H2O, 2,2′‐bipyridine (bpy), suberic acid and Na2CO3 in CH3OH/H2O yielded a mixture of Mn2(H2O)4(bpy)2(C8H12O4)2] · 2 H2O ( 1 ) and Mn(H2O)2‐ (bpy)(C8H12O4)2/2] · H2O ( 2 ). In both complexes, the Mn atoms are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two trans positioned H2O molecules and two suberato ligands (d(Mn–O) = 2.107–2.328 Å; d(Mn–N) = 2.250–2.330 Å). The bis‐monodentate suberato ligands bridge Mn atoms to form dinuclear Mn2(H2O)4(bpy)2(C8H12O4)2] complex molecules in 1 and 1D Mn(H2O)2(bpy)(C8H12O4)2/2] chains in 2 . Via the intermolecular hydrogen bondings and π‐π stacking interactions, the dinuclear molecules in 1 are assembled into 2D networks parallel to (100), between which the crystal H2O molecules are sandwiched. The polymeric chains in 2 are linked together by interchain hydrogen bonding and π‐π stacking interactions into 3D networks with the crystal H2O molecules located in tunnels along 010]. Crystal data for 1 : P21/c (no. 14), a = 10.092(1) Å, b = 11.916(2) Å, c = 17.296(2) Å, β = 93.41(1)° and Z = 2. Crystal data for 2 : P21/c (no. 14), a = 11.176(2) Å, b = 9.688(1) Å, c = 37.842(6) Å, β = 90.06(1)° and Z = 8. |