LiNb2O4 crystallizes in the orthorhombic Pnnm space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 pentagonal pyramids, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent Nb(1)O6 pentagonal pyramids. Nb(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted NbO6 pentagonal pyramids that share corners with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with six equivalent Nb(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-10°. There are two inequivalent O sites. In the first O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Nb(1) atoms. In the second O site, O(1) is bonded to two equivalent Li(1) and three equivalent Nb(1) atoms to form a mixture of edge and corner-sharing OLi2Nb3 square pyramids.
LiNb2O4 crystallizes in the orthorhombic Pnnm space group. Li(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with six equivalent Nb(1)O6 pentagonal pyramids, edges with two equivalent Li(1)O6 octahedra, and edges with six equivalent Nb(1)O6 pentagonal pyramids. Both Li(1)-O(2) bond lengths are 2.21 Å. All Li(1)-O(1) bond lengths are 2.19 Å. Nb(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form distorted NbO6 pentagonal pyramids that share corners with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with six equivalent Nb(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 6-10°. There are two shorter (2.13 Å) and one longer (2.14 Å) Nb(1)-O(1) bond length. There is one shorter (2.11 Å) and two longer (2.12 Å) Nb(1)-O(2) bond lengths. There are two inequivalent O sites. In the first O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent Nb(1) atoms. In the second O site, O(1) is bonded to two equivalent Li(1) and three equivalent Nb(1) atoms to form a mixture of edge and corner-sharing OLi2Nb3 square pyramids.