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A novel Cu(II)-2,2′-bipy-supported (bipy = bipyridine) mixed valence decatungstate, [Cu(2,2′-bipy)2]2Na2W6VW4VIO30·2H2O 1, has been synthesized and structurally characterized by X-ray analysis. The crystal of 1 is of triclinic, space group P1 with a