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The title compounds have been synthesized by reaction of the elements in sealed tantalum crucibles in a muffle furnace using special annealing sequences. The crystal structures of YbNi 2.31 Al 2.69  ( R 1 = 0.0100 for 212  F  2  values and 18 variables) and for ErNi 2.23 Al 2.77  ( R 1 = 0.0154 for 255  F  2  values and 18 variables) were refined from single crystal X-ray data. They belong to the YNi 2 Al 3  type ( i 3 superstructure of CaCu 5 ) with the following crystallographic parameters: space groupP  6   /   m  m  m$P6/mmm$, Pearson symbol  hP 18,  Z =  3,  a  = 8.2723(12),  c =  4.0672(8)   Å,  V  = 241.03(8)   Å 3  for YbNi 2.31 Al 2.69  and  a  = 8.9109(13),  c =  4.0669(8)   Å,  V  = 279.66(8)   Å 3  for ErNi 2.23 Al 2.77 . The crystal chemical discussion is supported by electronic structure calculations.

ErNi 2.23 Al 2.77 and YbNi 2.31 Al 2.69 – i 3 superstructures of the CaCu 5 type