A new organic–inorganic hybrid selenic vanadate [Cu(phen)(H2O)2][V3Se3O14] · H2O (1) has been hydrothermally synthesized and characterized by elemental analyses, IR, EPR spectra and the single crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group , a=6.3112(13) Å, b=13.249(3) Å, c=14.060(3) Å, α=100.88(3)°, β=90.48(3)°, γ=97.54(3)°, V=1143.9(4) Å3, Z=2, R1=0.0310. Compound 1 exhibits a novel 2-D selenic vanadate network on the basis of an unprecedented {V6Se6O28} oxide cluster building block. Furthermore, this new selenic vanadate layer is decorated by [Cu(phen)(H2O)2]2+ coordination complex fragments.
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