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In , synthetic chemistry of cyanidometalates started with the accidental discovery of Prussian blue, Fe 4 [Fe CN 6 ] 3 , a pigment with many additional applications still in use today.
Our quest for even higher reduced cyanidometalates containing other transition metals led to the ferrates and ruthenates LiSr 3 [Fe CN 3 ] and AE 3. NaN 3 was used instead of gaseous N 2 to control the nitrogen partial pressure during synthesis. It is closely related to that of Ba 3 [Co CN 3 ]. Closely related structure types are known for nitridometalates such as Ba 3 [FeN 3 ], which contains empty channels, [11] and acetylidemetalates such as La 3. This structure model yielded good figures of merit and a low residual electron density, but large and unusually oriented displacement ellipsoids especially for the carbon and nitrogen atoms.
Sr 9 [Fe CN 3 ] prisms are omitted in this view for simplicity reasons. Viewed along []. That is, half of the octahedral voids are filled with Ba5 atoms indicating a local alternating ordering within each light blue channel. Ba 9 [Fe CN 3 ] prisms are omitted in this picture for simplicity reasons, viewed along []. The acentric hexagonal crystal structure of Ba 3. The Ba 3. The divalent barium atoms alternately occupy half of the octahedra that form the channels along [].
This is a striking example of geometric frustration, since it is not possible to have a alternate ordering of the channels under hexagonal or trigonal symmetry.
