LiNbO3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Nb(1)O6 octahedra, corners with three equivalent Nb(2)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Nb(2)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-66°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Nb(2)O6 octahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-54°. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted NbO6 octahedra that share corners with two equivalent Nb(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Nb(1)O6 octahedra, edges with two equivalent Nb(2)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-27°. In the second Nb site, Nb(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Nb(1)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-27°. There are six inequivalent O sites. In the first O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(2), and two equivalent Nb(1) atoms. In the second O site, O(6) is bonded to one Li(2), two equivalent Li(1), and one Nb(2) atom to form distorted OLi3Nb trigonal pyramids that share corners with two equivalent O(2)Li2Nb2 trigonal pyramids, corners with two equivalent O(3)Li2Nb2 trigonal pyramids,  an edgeedge with one O(2)Li2Nb2 trigonal pyramid,  an edgeedge with one O(3)Li2Nb2 trigonal pyramid, and  an edgeedge with one O(6)Li3Nb trigonal pyramid. In the third O site, O(1) is bonded in a T-shaped geometry to one Li(2), one Nb(1), and one Nb(2) atom. In the fourth O site, O(2) is bonded to one Li(1), one Li(2), one Nb(1), and one Nb(2) atom to form distorted OLi2Nb2 trigonal pyramids that share corners with two equivalent O(6)Li3Nb trigonal pyramids,  an edgeedge with one O(6)Li3Nb trigonal pyramid, and edges with two equivalent O(3)Li2Nb2 trigonal pyramids. In the fifth O site, O(3) is bonded to one Li(1), one Li(2), one Nb(1), and one Nb(2) atom to form OLi2Nb2 trigonal pyramids that share corners with two equivalent O(6)Li3Nb trigonal pyramids,  an edgeedge with one O(6)Li3Nb trigonal pyramid, and edges with two equivalent O(2)Li2Nb2 trigonal pyramids. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Nb(1), and one Nb(2) atom.
LiNbO3 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Nb(1)O6 octahedra, corners with three equivalent Nb(2)O6 octahedra, corners with two equivalent Li(2)O5 trigonal bipyramids,  an edgeedge with one Nb(1)O6 octahedra,  an edgeedge with one Nb(2)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 26-66°. The Li(1)-O(2) bond length is 2.15 Å. The Li(1)-O(3) bond length is 2.02 Å. The Li(1)-O(4) bond length is 2.02 Å. There is one shorter (2.12 Å) and one longer (2.21 Å) Li(1)-O(6) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(5), and one O(6) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Nb(1)O6 octahedra,  a cornercorner with one Nb(2)O6 octahedra, corners with two equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Nb(1)O6 octahedra, edges with two equivalent Nb(2)O6 octahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-54°. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(2) bond length is 2.04 Å. The Li(2)-O(3) bond length is 2.28 Å. The Li(2)-O(5) bond length is 1.97 Å. The Li(2)-O(6) bond length is 1.90 Å. There are two inequivalent Nb sites. In the first Nb site, Nb(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form distorted NbO6 octahedra that share corners with two equivalent Nb(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(2)O5 trigonal bipyramid,  an edgeedge with one Nb(1)O6 octahedra, edges with two equivalent Nb(2)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-27°. The Nb(1)-O(1) bond length is 1.88 Å. The Nb(1)-O(2) bond length is 1.95 Å. The Nb(1)-O(3) bond length is 2.13 Å. The Nb(1)-O(4) bond length is 1.96 Å. There is one shorter (2.00 Å) and one longer (2.19 Å) Nb(1)-O(5) bond length. In the second Nb site, Nb(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted NbO6 octahedra that share corners with two equivalent Nb(1)O6 octahedra,  a cornercorner with one Li(2)O5 trigonal bipyramid, corners with three equivalent Li(1)O5 trigonal bipyramids, edges with two equivalent Nb(1)O6 octahedra,  an edgeedge with one Li(1)O5 trigonal bipyramid, and edges with two equivalent Li(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 25-27°. The Nb(2)-O(1) bond length is 2.07 Å. The Nb(2)-O(2) bond length is 2.04 Å. The Nb(2)-O(3) bond length is 1.93 Å. The Nb(2)-O(4) bond length is 2.03 Å. The Nb(2)-O(5) bond length is 2.30 Å. The Nb(2)-O(6) bond length is 1.83 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a rectangular see-saw-like geometry to one Li(2), one Nb(2), and two equivalent Nb(1) atoms. In the second O site, O(6) is bonded to one Li(2), two equivalent Li(1), and one Nb(2) atom to form distorted OLi3Nb trigonal pyramids that share corners with two equivalent O(2)Li2Nb2 trigonal pyramids, corners with two equivalent O(3)Li2Nb2 trigonal pyramids,  an edgeedge with one O(2)Li2Nb2 trigonal pyramid,  an edgeedge with one O(3)Li2Nb2 trigonal pyramid, and  an edgeedge with one O(6)Li3Nb trigonal pyramid. In the third O site, O(1) is bonded in a T-shaped geometry to one Li(2), one Nb(1), and one Nb(2) atom. In the fourth O site, O(2) is bonded to one Li(1), one Li(2), one Nb(1), and one Nb(2) atom to form distorted OLi2Nb2 trigonal pyramids that share corners with two equivalent O(6)Li3Nb trigonal pyramids,  an edgeedge with one O(6)Li3Nb trigonal pyramid, and edges with two equivalent O(3)Li2Nb2 trigonal pyramids. In the fifth O site, O(3) is bonded to one Li(1), one Li(2), one Nb(1), and one Nb(2) atom to form OLi2Nb2 trigonal pyramids that share corners with two equivalent O(6)Li3Nb trigonal pyramids,  an edgeedge with one O(6)Li3Nb trigonal pyramid, and edges with two equivalent O(2)Li2Nb2 trigonal pyramids. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Li(1), one Nb(1), and one Nb(2) atom.