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The analysis of cation sublattices population in magnesium doped LiNbO_{3} crystals is carried out. It is shown that volume concentration of lithium vacancies (V_{Li}) monotonously increases with increasing of MgO content in the crystal up to the threshold value. A series of LiNbO_{3} crystals with various concentration of Mg^{2+} were investigated by ^{7}Li and ^{93}Nb Nuclear Magnetic Resonance (NMR). It is concluded that the peculiarities of NMR spectra in Mg-doped LiNbO_{3} crystals can be explained by the formation of defect complexes including Mg_{Li} ions and V_{Li} on the shortest distances between them.
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