Two novel 1D chains based on heptacoordinated Mn(II) ions bridged by variously derived benzoate ligands were prepared. The unusual structures of [Mn^II(L¹)(L²)₄]_n1 and [Mn^II(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.