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Crystal structures of nonstoichiometric La(Ni, Sn)5+x (x = 0.1～0.4) alloys prepared by different methods were investigated by using powder X-ray diffraction and Rietveld refinement analysis. Space group of this type of alloys belongs to P6/mmm, in which Sn only occupies the 3g sites. It has been demonstrated that some of the 1a sites of the nonstoichiometric alloy are replaced by the Ni-Ni dumb-bells which have a strong correlation with the anisotropic thermal parameter B33. The preparation methods have an effect on the number of dumb-bells that can substitute the 1a sites. It was found that the annealed alloys have more Ni-Ni dumb-bells in the structure than the rapid solidified and as-cast alloys have while still keep good crystallinity.