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Despite the fact that both nitrosonium salts NO[SbCl 6 ] and NO[TaCl 6 ] crystallize in the same space group  C 2/ c  with  Z  = 4, their disorder behaviour is different. While in the antimony compound the reorientation jumps of the NO +  ions are restricted to two alignments of equal weight, the NO +  disorder of NO[TaCl 6 ] is in principle six fold, but with two of the alignments underrepresented. NO[SbCl 6 ] undergoes a phase transformation to  C -1 at  T  c  = 104 K. NO[TaCl 6 ] stays monoclinic down to 10 K. An extrapolation of the isotropic displacements against abso lute zero reveals permanent components due to genuine dis order. A computer simulation is used to investigate the unusual population of the NO +  sites.

The crystal structures and the disorder behaviour of NO[SbCl 6 ] and NO[TaCl 6 ]