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Three members of a new family of phases, Li3Mg2XO6: X = Nb, Ta, Sb, have been prepared by solid-state reaction of MgO and Li3XO4. Unit-cell parameters of Li3Mg2TaO6 determined by electron diffraction and refined by X-ray powder diffraction are a = 8.883(2), b = 5.802(2), c = 17.437(6) Å, with space group Fddd; z = 8. Powder diffraction data of Li3Mg2NbO6 and Li3Mg2SbO6 were indexed by analogy with those of Li3Mg2TaO6 and unit-cell dimensions obtained by least-squares refinement: Li3Mg2NbO6 a = 8.552(2), b = 5.897(1), c = 17.721(5) Å; Li3Mg2SbO6 a = 8.614 (1), b = 5.908(1), c = 17.759(5) Å.

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