Hans‐Jürgen Meyer

The tetracyanamidometallates Li 4 [ T (CN 2 ) 4 ] with T =Si, Ge were prepared by solid‐state metathesis (SSM) reactions between T I 4 and Li 2 (CN 2 ). The new compounds Li 4 [ T (CN 2 ) 4 ] are obtained as crystalline phases in high yields and represent the most basic examples of the family of tetracyanamidometallates. The formation of these compounds, via SiI 4 and Li 2 (CN 2 ), is analyzed by means of differential scanning calorimetry (DSC). The [Si(CN 2 ) 4 ] 4− ion in the structure of Li 4 [Si(CN 2 ) 4 ] can be considered an analogue to the [SiO 4 ] 4− ion in Li 4 SiO 4 . The crystal structures of Li 4 [ T (CN 2 ) 4 ] were solved and refined isotypically on the basis of single‐crystal X‐ray diffraction data in the space group C 2/ c , and further characterized by infrared and solid‐state NMR techniques.