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Double perovskites Ba1+xLa1−xMnSbO6 were synthesized by traditional ceramic methods in air as polycrystalline powders. The 0.1 ≤ x ≤ 0.2 compounds belong to the I 2/m monoclinic space group, while the perovskites with x ≥ 0.3 belong to the I 4/m tetragonal space group. The effective presence of mixtures of Mn2+/Mn3+ has been well established by X-ray Emission Spectroscopy. Ba1+xLa1−xMnSbO6 (0.1 ≤ x ≤ 0...