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A one-dimensional polyoxotungstate, Na(H2O)2[Co(en)3]3H3[Co4(H2O)2(B-α-PW9O34)2]·10.5H2O(en=ethylenediamine), was hydrothermally synthesized and characterized by single crystal X-ray diffraction,infrared spectroscopy,thermogravimetric analysis,and powder X-ray diffraction, respectively.The structure was constructed from the[Co4(H2O)2(B-α-PW9O34)2]- units, in which a tetra-cobalt cluster core was sandwiched between two PW9O349- polyanions,that were further connected via Na+ cations forming a one-dimensional chain structure.