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A novel Mg(II) complex, [Mg(HL)2•(H2O)4]•4H2O•HCl (HL = 1,2-phenylenedioxydiacetato), has been synthesized by the reaction of 1,2-phenylenedioxydiacetic acid, NaOH and MgCl2•6H2O in one-pot. The compound was characterized by X-ray single crystal diffraction analysis. The crystal of the title complex belongs to monoclinic, space group Pn with a = 10.772(2) Å, b = 9.7145(19) Å, c = 13.996(3) Å, β = 104.32(3)º, V = 1419.1(5) Å3, Z = 2, Dc = 1.498 μg•m-3, μ = 0.245 mm-1, F(000) = 658 and final R1 = 0.0653, ωR2 = 0.1913. The molecules are connected by π-π stacking to form three dimensional network structures.