Abstract: | The triclinic superstructure of a small crystal of LiCa2Nb3O10, lithium dicalcium triniobium decaoxide, has been investigated by synchrotron X‐ray diffraction. The unit cell is an almost rectangular parallelepiped, although there is a 0.245° offset from orthogonality for β. The structure essentially belongs to a homologous series of LiNan?3Ca2NbnO3n+1] with n = 3, where the moiety in square brackets has a perovskite‐type slab structure. The superstructure has a doubled unit‐cell volume with respect to the tetragonal aristotype. The NbO6 octahedra are rotated about axes parallel to 110] by approximately 10°. Adjacent slabs are connected by Li atoms and are geometrically related by 42 pseudosymmetry lying parallel to c . There are twice as many sites as Li atoms, providing a variation of population at these Li sites. |