LiNb2(PO5)2 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 69°. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NbO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-69°. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra and corners with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-61°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Nb(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Nb(1) atoms.
LiNb2(PO5)2 crystallizes in the monoclinic C2/m space group. Li(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form distorted LiO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and faces with two equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles are 69°. Both Li(1)-O(3) bond lengths are 2.46 Å. All Li(1)-O(2) bond lengths are 2.03 Å. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NbO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra, corners with two equivalent Nb(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  a faceface with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-69°. Both Nb(1)-O(1) bond lengths are 2.02 Å. Both Nb(1)-O(2) bond lengths are 2.12 Å. There is one shorter (1.82 Å) and one longer (2.34 Å) Nb(1)-O(3) bond length. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra and corners with four equivalent Nb(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-61°. Both P(1)-O(1) bond lengths are 1.54 Å. Both P(1)-O(2) bond lengths are 1.55 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Nb(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Nb(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1) and two equivalent Nb(1) atoms.