A new structural model is proposed for cubic nitroprussides and the crystal structure for the complex salts of Fe(2+), Co(2+), and Ni(2+) refined in that model. In cubic nitroprussides the building unit, [Fe(CN)5NO]2−, and the assembling metal (M=Fe2+,Co2+,Ni2+), have ¾ occupancy with three formula units per cell (Z=3). This leads to certain structural disorder and to different local environments for the outer metal. The crystallographic results are supported by the Mössbauer and infrared data. The XRD powder patterns, index in a cubic cell (Fm3m space group), show a sinuous background because of diffuse scattering from positional disorder of the metal centers. Because of this, the crystal structures were refined allowing the metal centers to move from the (0,0,0) and (0,0,1/2) positions (away from positional symmetry restrictions). The refinement under these conditions leads to excellent agreement factors (Rwp, Rp, S), good pattern background fitting, and produced a refined structural model consistent with the crystal chemistry of nitroprussides. The studied materials are obtained as hydrates. On heating, the crystal water evolves, and below 100°C an anhydrous phase is obtained, preserving the framework of the original hydrates. The loss of the crystal water leads to cell contraction that represents around 2% of cell volume reduction. On cooling down from room temperature to 77 and 12 K, a slight expansion for the -M-N≡C-Fe-C≡N-M- chain length is observed, suggesting that at low temperature and reduction in the metals charge delocalization on the CN bridges takes place. For M=Fe and Co the crystal structure was also refined for the anhydrous phase at 12, 77, and 300 K.
