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The structure of the title compound, [Mg(C10H6O6S2)(C3H7NO)2]n, consists of MgO6 octa­hedra (\overline{1} symmetry) connected to naphthalene-1,5-disulfonate ligands (\overline{1} symmetry) in the equatoral plane, forming a two-dimensional network propagating parallel to (010). The coordination sphere of the Mg atom is completed by the O atoms of two N,N-dimethyl­formamide (DMF) mol­ecules in the axial positions. The title compound represents the first time the naphthalene-1,5-disulfonate anion is bound directly to a Mg2+ atom. Disorder over two positions was found in the DMF mol­ecule in a 0.518 (8):0.482 (8) ratio.
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