Slab Rotation by Transition‐Metal Relocation in the Layered Zintl Phase Li₂ZnSi

The layered Zintl phase Li 2 ZnSi is a structural analog of intercalated graphite with hexagonal layers of Zn and Si atoms separated by Li atoms (space group P 6 3 / mmc , a = 4.2458(2) Å, c = 8.224(1) Å). Single‐crystal X‐ray diffraction reveals Zn relocation into the center of the Zn 3 Si 3 rings in 4% of the hexagonal layers. The Zn relocation is coupled with Li migration. The resulting 2D defects can be modeled either as 60° slab rotations or, alternatively, as layer translations by k = 1/3 [1,−1,0]. Li 2 ZnSi shows metal‐type electrical resistivity (ρ = 1.18 μΩ m at 300 K) and exhibits significantly enhanced diamagnetism, suggesting orbital contributions akin to those in graphite. This study demonstrates transition‐metal mobility in a layered Zintl phase, generating localized 2D defects that leave the local coordination of each atom unchanged. This mechanism is relevant for understanding defect tolerance in structurally related electrode materials.