The first single-crystal X-ray structural refinement of the superconducting phase Li0.2(1) ZrNCl derived by intercalation

The single crystals of the superconducting Li_0.2(1)ZrNCl have been derived from the single crystals of β-ZrNCl by intercalation of lithium using an n-butyllithium solution in hexane. The crystal structure has been refined on the basis of the single-crystal X-ray data: the space group R-3m, a=3.591(1) Å, c=27.839(6) Å, Z=6, R1=0.0749 for 196 reflections and 12 variables. β-ZrNCl is isotypic with SmSI, while the structure of Li_0.2(1)ZrNCl can be described as the Li intercalated YOF type, a stacking variant of the SmSI type. The tightly bound slabs with a Cl-Zr-N-N-Zr-Cl sequence of close-packed layers are stacked rhombohedrally along the c-axis, with the van der Waals gaps between the chlorine layers hosting Li ions. This is the first single-crystal study on the Li intercalated phase. The structural changes from the pristine single crystals were precisely determined.