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А novel manganese(II) coordination polymer, catena-(2-methylimidazolium bis(μ2-chloro)aquachloromanganese(II)), {(C4H7N2)[MnCl3(H2O)]}n, was synthesized, structurally characterized by FTIR spectroscopy and confirmed by single crystal X-ray diffraction analysis. Thermogravimetric analysis and EPR spectroscopy of the compound were also performed. The colourless crystals of the complex were monoclinic, space group P21/c, with the cell parameters a = 11.298(2) Å, b = 7.2485(14) Å, c = 14.709(5) Å, β = 128.861(18)°, V = 938.0(5) Å3, Z = 4 and R1 = 0.03. The title compound consisted of one-dimensional infinite anionic chains [MnCl3(H2O)]n and isolated 2-methylimidazolium cations. The Mn(II) atom was octahedrally coordinated to four bridging chloride anions (Mn–Cl = 2.5109(6) – 2.5688(7) Å), one terminal chloride anion (Mn–Cl = 2.5068(11) Å) and a H2O molecule (Mn–O = 2.2351(17) Å). A three-dimensional layer structure was constructed via hydrogen bonds and by weak π–π stacking interactions. A four-step thermal decomposition occurred in the temperature range 25–900 °C under nitrogen.