Two novel 1D chains based on heptacoordinated Mn(II) ions bridged by variously derived benzoate ligands were prepared. The unusual structures of [MnII(L1)(L2)4]n1 and [MnII(L1)(L3)4]n2 (where L1 = 2,6-dimethanolpyridine, L2 = 3,5-dinitrobenzoic acid, L3 = 4-chloro-3,5-dinitrobenzoic acid) were confirmed by single-crystal X-ray diffraction. Within the structures a zig zag pattern appears from perpendicularly located 2,6-dimethanolpyridines to sheets of benzoic acids. Both compounds possess the {MnNO6} chromophore and show paramagnetic behaviour with an exchange interaction of antiferromagnetic nature. Weak interaction constants J/hc = −0.54 cm−1 (1) and J/hc = −0.58 cm−1 (2) between high spin (S = 5/2) magnetic centres have been revealed using a finite-ring Hamiltonian model. [ABSTRACT FROM AUTHOR]