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A new niobate crystal Ba4Na2VNb9O30 was synthesized in BaO-Na2O-V2O5-Nb2O5 system for the first time.Its shape,optical properties,melting point and chemical stability were studied.X-ray powder diffraction study determined that this compound assumes a tetragonal tungsten bronze structure with space group P4bm(100) and lattice parameters a=b=12.4275(2),c=3.970(3).The new compound may be one kind of photorefractive crystals.