Absence of van der Waals Gap in Ternary Thorium Nitride ThNF and ThNCl

Two kinds of ternary thorium nitride compounds, ThNF and ThNCl, are synthesized. Via the refinement of X-ray diffraction patterns, the accurate crystal structure of the two compounds is solved. Although ThNF and ThNCl share a similar structure with MNX (M = Ti, Zr, Hf; X = Cl, Br) compounds, the interaction between adjacent ThNF and ThNCl layers is not a van der Waals gap. For ThNF, the strong electronegativity of F ions leads to the bonding of Th to the F both in the nearest neighbor layer and the next nearest neighbor layer, which results in the absence of a van der Waals gap between ThNF layers. However, for ThNCl, the reason for the absence of a van der Waals gap could be attributed to the large Th-Cl bond length due to the partially covalent Th-Cl bond as well as the flat ThN layer. It is the absence of van der Waals gap that results in the failure of intercalating cations into ThNF and ThNCl. Our result reveals the reason for unsuccessful intercalation in ThNF and ThNCl, thereby providing a deeper understanding for the interlayer interaction in ternary layer structures in metal nitride halides.