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The salt crystallizes in the <jats:italic>P<\/jats:italic>2<jats:sub>1<\/jats:sub>\/<jats:italic>n<\/jats:italic> space group. Imidazole, initially used in the synthesis but not present in the product, and DMF solvent appear to affect the synthesis and crystallization as structural-directing agents. In the title compound, the complex cation [Zn(H<jats:sub>2<\/jats:sub>O)<jats:sub>5<\/jats:sub>(DMF)]<jats:sup>2+<\/jats:sup> acts as a counter-ion without being directly coordinated to the decavanadate anion. An extensive framework of hydrogen bonds integrates the whole architecture as evidenced by X-ray crystallography. 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