Li6Mo2O7 crystallizes in the orthorhombic Pma2 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), two equivalent O(1), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with four equivalent Mo(2)O6 octahedra,  a cornercorner with one Li(5)O5 square pyramid, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 4-10°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with four equivalent Mo(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 2-6°. In the third Li site, Li(3) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with four equivalent Li(5)O5 square pyramids, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. In the fourth Li site, Li(4) is bonded in a see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. In the fifth Li site, Li(5) is bonded to one O(5), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 square pyramids that share corners with four equivalent Li(3)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 9-11°. In the sixth Li site, Li(6) is bonded in a see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 2-6°. In the second Mo site, Mo(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Mo(1), and one Mo(2) atom to form OLi4Mo2 octahedra that share corners with two equivalent O(1)Li4Mo2 octahedra, corners with four equivalent O(2)Li5Mo octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(1)Li4Mo2 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with two equivalent O(2)Li5Mo octahedra, and edges with two equivalent O(3)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 1-16°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Li(6), and one Mo(2) atom to form OLi5Mo octahedra that share corners with two equivalent O(2)Li5Mo octahedra, corners with four equivalent O(1)Li4Mo2 octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(1)Li4Mo2 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with two equivalent O(2)Li5Mo octahedra, and edges with two equivalent O(3)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 1-16°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(4), two equivalent Li(6), and one Mo(2) atom to form OLi5Mo octahedra that share corners with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(3)Li5Mo octahedra, edges with four equivalent O(1)Li4Mo2 octahedra, and edges with four equivalent O(2)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(2), one Mo(2), and two equivalent Mo(1) atoms to form OLi3Mo3 octahedra that share corners with two equivalent O(3)Li5Mo octahedra, corners with four equivalent O(5)Li4Mo2 octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with four equivalent O(1)Li4Mo2 octahedra, and edges with four equivalent O(2)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fifth O site, O(5) is bonded to one Li(1), one Li(5), two equivalent Li(2), and two equivalent Mo(1) atoms to form OLi4Mo2 octahedra that share corners with four equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with four equivalent O(1)Li4Mo2 octahedra, and edges with four equivalent O(2)Li5Mo octahedra. The corner-sharing octahedral tilt angles are 4°.
Li6Mo2O7 crystallizes in the orthorhombic Pma2 space group. There are six inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(5), two equivalent O(1), and two equivalent O(2) atoms to form distorted LiO5 square pyramids that share corners with four equivalent Mo(2)O6 octahedra,  a cornercorner with one Li(5)O5 square pyramid, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 4-10°. The Li(1)-O(5) bond length is 1.95 Å. Both Li(1)-O(1) bond lengths are 2.46 Å. Both Li(1)-O(2) bond lengths are 2.13 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with four equivalent Mo(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 2-6°. Both Li(2)-O(2) bond lengths are 2.28 Å. Both Li(2)-O(4) bond lengths are 2.17 Å. Both Li(2)-O(5) bond lengths are 2.11 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with four equivalent Li(5)O5 square pyramids, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. The Li(3)-O(3) bond length is 2.06 Å. The Li(3)-O(4) bond length is 2.36 Å. Both Li(3)-O(1) bond lengths are 2.20 Å. Both Li(3)-O(2) bond lengths are 2.17 Å. In the fourth Li site, Li(4) is bonded in a see-saw-like geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Li(4)-O(1) bond lengths are 2.08 Å. Both Li(4)-O(3) bond lengths are 1.97 Å. In the fifth Li site, Li(5) is bonded to one O(5), two equivalent O(1), and two equivalent O(2) atoms to form LiO5 square pyramids that share corners with four equivalent Li(3)O6 octahedra,  a cornercorner with one Li(1)O5 square pyramid, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, and edges with two equivalent Li(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 9-11°. The Li(5)-O(5) bond length is 2.00 Å. Both Li(5)-O(1) bond lengths are 2.14 Å. Both Li(5)-O(2) bond lengths are 2.14 Å. In the sixth Li site, Li(6) is bonded in a see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(6)-O(2) bond lengths are 2.00 Å. Both Li(6)-O(3) bond lengths are 1.96 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, edges with two equivalent Mo(2)O6 octahedra, edges with two equivalent Li(1)O5 square pyramids, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 2-6°. Both Mo(1)-O(1) bond lengths are 2.19 Å. Both Mo(1)-O(4) bond lengths are 2.19 Å. Both Mo(1)-O(5) bond lengths are 2.12 Å. In the second Mo site, Mo(2) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MoO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(1)O5 square pyramids, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Mo(1)O6 octahedra, and edges with two equivalent Li(5)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-6°. The Mo(2)-O(3) bond length is 1.98 Å. The Mo(2)-O(4) bond length is 2.12 Å. Both Mo(2)-O(1) bond lengths are 2.09 Å. Both Mo(2)-O(2) bond lengths are 1.96 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(4), one Li(5), one Mo(1), and one Mo(2) atom to form OLi4Mo2 octahedra that share corners with two equivalent O(1)Li4Mo2 octahedra, corners with four equivalent O(2)Li5Mo octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(1)Li4Mo2 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with two equivalent O(2)Li5Mo octahedra, and edges with two equivalent O(3)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 1-16°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one Li(5), one Li(6), and one Mo(2) atom to form OLi5Mo octahedra that share corners with two equivalent O(2)Li5Mo octahedra, corners with four equivalent O(1)Li4Mo2 octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(1)Li4Mo2 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with two equivalent O(2)Li5Mo octahedra, and edges with two equivalent O(3)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 1-16°. In the third O site, O(3) is bonded to one Li(3), two equivalent Li(4), two equivalent Li(6), and one Mo(2) atom to form OLi5Mo octahedra that share corners with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(3)Li5Mo octahedra, edges with four equivalent O(1)Li4Mo2 octahedra, and edges with four equivalent O(2)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to one Li(3), two equivalent Li(2), one Mo(2), and two equivalent Mo(1) atoms to form OLi3Mo3 octahedra that share corners with two equivalent O(3)Li5Mo octahedra, corners with four equivalent O(5)Li4Mo2 octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with four equivalent O(1)Li4Mo2 octahedra, and edges with four equivalent O(2)Li5Mo octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fifth O site, O(5) is bonded to one Li(1), one Li(5), two equivalent Li(2), and two equivalent Mo(1) atoms to form OLi4Mo2 octahedra that share corners with four equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(4)Li3Mo3 octahedra, edges with two equivalent O(5)Li4Mo2 octahedra, edges with four equivalent O(1)Li4Mo2 octahedra, and edges with four equivalent O(2)Li5Mo octahedra. The corner-sharing octahedral tilt angles are 4°.