Li5W2O7 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(7), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(4)O5 square pyramid, corners with four equivalent Li(5)O5 square pyramids,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra,  an edgeedge with one Li(5)O5 square pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 7-78°. In the second Li site, Li(2) is bonded to one O(3), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O5 square pyramids, corners with three equivalent Li(4)O5 square pyramids,  a cornercorner with one Li(1)O5 trigonal bipyramid,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent W(2)O6 octahedra, and edges with two equivalent Li(4)O5 square pyramids. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom. In the fourth Li site, Li(4) is bonded to one O(5), one O(6), one O(7), and two equivalent O(2) atoms to form LiO5 square pyramids that share  a cornercorner with one W(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent W(2)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid, and  an edgeedge with one Li(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-84°. In the fifth Li site, Li(5) is bonded to one O(4), one O(5), one O(7), and two equivalent O(1) atoms to form LiO5 square pyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid,  an edgeedge with one Li(5)O5 square pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 8-87°. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(3), one O(6), one O(7), and two equivalent O(4) atoms to form WO6 octahedra that share  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one Li(5)O5 square pyramid, corners with two equivalent Li(4)O5 square pyramids, corners with two equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent W(2)O6 octahedra, edges with two equivalent Li(5)O5 square pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 14°. In the second W site, W(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one Li(5)O5 square pyramid,  a cornercorner with one Li(1)O5 trigonal bipyramid, edges with two equivalent W(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(5)O5 square pyramid, edges with two equivalent Li(4)O5 square pyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 14°. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(5), and one W(1) atom to form OLi5W octahedra that share  a cornercorner with one O(2)Li5W octahedra,  a cornercorner with one O(5)Li5W octahedra, corners with two equivalent O(4)Li2W3 square pyramids, corners with two equivalent O(3)Li3W2 square pyramids,  an edgeedge with one O(5)Li5W octahedra, edges with two equivalent O(1)Li5W octahedra,  an edgeedge with one O(3)Li3W2 square pyramid, edges with two equivalent O(4)Li2W3 square pyramids, and  an edgeedge with one O(6)Li3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 6-12°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), two equivalent Li(4), and one W(2) atom to form OLi5W octahedra that share  a cornercorner with one O(1)Li5W octahedra, corners with two equivalent O(5)Li5W octahedra,  a cornercorner with one O(4)Li2W3 square pyramid, corners with two equivalent O(6)Li3W2 trigonal bipyramids, edges with two equivalent O(2)Li5W octahedra, edges with three equivalent O(5)Li5W octahedra, edges with two equivalent O(3)Li3W2 square pyramids, and edges with two equivalent O(6)Li3W2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-11°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one W(1), and one W(2) atom to form distorted OLi3W2 square pyramids that share corners with two equivalent O(1)Li5W octahedra, corners with two equivalent O(5)Li5W octahedra, corners with two equivalent O(4)Li2W3 square pyramids, corners with two equivalent O(6)Li3W2 trigonal bipyramids,  an edgeedge with one O(1)Li5W octahedra,  an edgeedge with one O(5)Li5W octahedra, edges with two equivalent O(2)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid, and  an edgeedge with one O(6)Li3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 1-88°. In the fourth O site, O(4) is bonded to one Li(1), one Li(5), one W(2), and two equivalent W(1) atoms to form distorted OLi2W3 square pyramids that share  a cornercorner with one O(2)Li5W octahedra, corners with two equivalent O(1)Li5W octahedra, corners with two equivalent O(3)Li3W2 square pyramids,  a cornercorner with one O(6)Li3W2 trigonal bipyramid,  an edgeedge with one O(5)Li5W octahedra, edges with two equivalent O(1)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid,  an edgeedge with one O(3)Li3W2 square pyramid, and  an edgeedge with one O(6)Li3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 8-80°. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Li(5), two equivalent Li(2), and one W(2) atom to form OLi5W octahedra that share  a cornercorner with one O(1)Li5W octahedra, corners with two equivalent O(2)Li5W octahedra, corners with two equivalent O(3)Li3W2 square pyramids,  a cornercorner with one O(6)Li3W2 trigonal bipyramid,  an edgeedge with one O(1)Li5W octahedra,  an edgeedge with one O(5)Li5W octahedra, edges with three equivalent O(2)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid,  an edgeedge with one O(3)Li3W2 square pyramid, and edges with two equivalent O(6)Li3W2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-12°. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one Li(4), one W(1), and one W(2) atom to form distorted OLi3W2 trigonal bipyramids that share  a cornercorner with one O(5)Li5W octahedra, corners with two equivalent O(2)Li5W octahedra,  a cornercorner with one O(4)Li2W3 square pyramid, corners with two equivalent O(3)Li3W2 square pyramids,  an edgeedge with one O(1)Li5W octahedra, edges with two equivalent O(2)Li5W octahedra, edges with two equivalent O(5)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid, and  an edgeedge with one O(3)Li3W2 square pyramid. The corner-sharing octahedral tilt angles range from 14-81°. In the seventh O site, O(7) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one W(1), and one W(2) atom.
Li5W2O7 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3), one O(4), one O(7), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(4)O5 square pyramid, corners with four equivalent Li(5)O5 square pyramids,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra,  an edgeedge with one Li(5)O5 square pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 7-78°. The Li(1)-O(3) bond length is 2.10 Å. The Li(1)-O(4) bond length is 2.33 Å. The Li(1)-O(7) bond length is 2.20 Å. There is one shorter (1.95 Å) and one longer (2.10 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded to one O(3), one O(6), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(5)O5 square pyramids, corners with three equivalent Li(4)O5 square pyramids,  a cornercorner with one Li(1)O5 trigonal bipyramid,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent W(2)O6 octahedra, and edges with two equivalent Li(4)O5 square pyramids. The Li(2)-O(3) bond length is 2.13 Å. The Li(2)-O(6) bond length is 2.15 Å. There is one shorter (2.08 Å) and one longer (2.21 Å) Li(2)-O(2) bond length. There is one shorter (2.15 Å) and one longer (2.48 Å) Li(2)-O(5) bond length. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom. The Li(3)-O(1) bond length is 2.26 Å. The Li(3)-O(2) bond length is 2.06 Å. The Li(3)-O(3) bond length is 2.10 Å. The Li(3)-O(5) bond length is 2.20 Å. The Li(3)-O(6) bond length is 2.14 Å. The Li(3)-O(7) bond length is 2.60 Å. In the fourth Li site, Li(4) is bonded to one O(5), one O(6), one O(7), and two equivalent O(2) atoms to form LiO5 square pyramids that share  a cornercorner with one W(2)O6 octahedra, corners with two equivalent W(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent W(2)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid, and  an edgeedge with one Li(5)O5 square pyramid. The corner-sharing octahedral tilt angles range from 3-84°. The Li(4)-O(5) bond length is 2.17 Å. The Li(4)-O(6) bond length is 2.07 Å. The Li(4)-O(7) bond length is 2.22 Å. There is one shorter (2.12 Å) and one longer (2.13 Å) Li(4)-O(2) bond length. In the fifth Li site, Li(5) is bonded to one O(4), one O(5), one O(7), and two equivalent O(1) atoms to form LiO5 square pyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one W(2)O6 octahedra, edges with two equivalent W(1)O6 octahedra,  an edgeedge with one Li(4)O5 square pyramid,  an edgeedge with one Li(5)O5 square pyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 8-87°. The Li(5)-O(4) bond length is 2.19 Å. The Li(5)-O(5) bond length is 2.11 Å. The Li(5)-O(7) bond length is 2.12 Å. There is one shorter (2.08 Å) and one longer (2.16 Å) Li(5)-O(1) bond length. There are two inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(3), one O(6), one O(7), and two equivalent O(4) atoms to form WO6 octahedra that share  a cornercorner with one W(2)O6 octahedra,  a cornercorner with one Li(5)O5 square pyramid, corners with two equivalent Li(4)O5 square pyramids, corners with two equivalent Li(1)O5 trigonal bipyramids,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one W(1)O6 octahedra, edges with two equivalent W(2)O6 octahedra, edges with two equivalent Li(5)O5 square pyramids, and edges with two equivalent Li(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 14°. The W(1)-O(1) bond length is 1.97 Å. The W(1)-O(3) bond length is 2.11 Å. The W(1)-O(6) bond length is 2.12 Å. The W(1)-O(7) bond length is 2.10 Å. There is one shorter (2.09 Å) and one longer (2.18 Å) W(1)-O(4) bond length. In the second W site, W(2) is bonded to one O(2), one O(3), one O(4), one O(5), one O(6), and one O(7) atom to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one Li(4)O5 square pyramid,  a cornercorner with one Li(5)O5 square pyramid,  a cornercorner with one Li(1)O5 trigonal bipyramid, edges with two equivalent W(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra,  an edgeedge with one Li(5)O5 square pyramid, edges with two equivalent Li(4)O5 square pyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 14°. The W(2)-O(2) bond length is 1.96 Å. The W(2)-O(3) bond length is 2.09 Å. The W(2)-O(4) bond length is 2.16 Å. The W(2)-O(5) bond length is 1.88 Å. The W(2)-O(6) bond length is 2.04 Å. The W(2)-O(7) bond length is 2.06 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(5), and one W(1) atom to form OLi5W octahedra that share  a cornercorner with one O(2)Li5W octahedra,  a cornercorner with one O(5)Li5W octahedra, corners with two equivalent O(4)Li2W3 square pyramids, corners with two equivalent O(3)Li3W2 square pyramids,  an edgeedge with one O(5)Li5W octahedra, edges with two equivalent O(1)Li5W octahedra,  an edgeedge with one O(3)Li3W2 square pyramid, edges with two equivalent O(4)Li2W3 square pyramids, and  an edgeedge with one O(6)Li3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 6-12°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(2), two equivalent Li(4), and one W(2) atom to form OLi5W octahedra that share  a cornercorner with one O(1)Li5W octahedra, corners with two equivalent O(5)Li5W octahedra,  a cornercorner with one O(4)Li2W3 square pyramid, corners with two equivalent O(6)Li3W2 trigonal bipyramids, edges with two equivalent O(2)Li5W octahedra, edges with three equivalent O(5)Li5W octahedra, edges with two equivalent O(3)Li3W2 square pyramids, and edges with two equivalent O(6)Li3W2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-11°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one W(1), and one W(2) atom to form distorted OLi3W2 square pyramids that share corners with two equivalent O(1)Li5W octahedra, corners with two equivalent O(5)Li5W octahedra, corners with two equivalent O(4)Li2W3 square pyramids, corners with two equivalent O(6)Li3W2 trigonal bipyramids,  an edgeedge with one O(1)Li5W octahedra,  an edgeedge with one O(5)Li5W octahedra, edges with two equivalent O(2)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid, and  an edgeedge with one O(6)Li3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 1-88°. In the fourth O site, O(4) is bonded to one Li(1), one Li(5), one W(2), and two equivalent W(1) atoms to form distorted OLi2W3 square pyramids that share  a cornercorner with one O(2)Li5W octahedra, corners with two equivalent O(1)Li5W octahedra, corners with two equivalent O(3)Li3W2 square pyramids,  a cornercorner with one O(6)Li3W2 trigonal bipyramid,  an edgeedge with one O(5)Li5W octahedra, edges with two equivalent O(1)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid,  an edgeedge with one O(3)Li3W2 square pyramid, and  an edgeedge with one O(6)Li3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 8-80°. In the fifth O site, O(5) is bonded to one Li(3), one Li(4), one Li(5), two equivalent Li(2), and one W(2) atom to form OLi5W octahedra that share  a cornercorner with one O(1)Li5W octahedra, corners with two equivalent O(2)Li5W octahedra, corners with two equivalent O(3)Li3W2 square pyramids,  a cornercorner with one O(6)Li3W2 trigonal bipyramid,  an edgeedge with one O(1)Li5W octahedra,  an edgeedge with one O(5)Li5W octahedra, edges with three equivalent O(2)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid,  an edgeedge with one O(3)Li3W2 square pyramid, and edges with two equivalent O(6)Li3W2 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 4-12°. In the sixth O site, O(6) is bonded to one Li(2), one Li(3), one Li(4), one W(1), and one W(2) atom to form distorted OLi3W2 trigonal bipyramids that share  a cornercorner with one O(5)Li5W octahedra, corners with two equivalent O(2)Li5W octahedra,  a cornercorner with one O(4)Li2W3 square pyramid, corners with two equivalent O(3)Li3W2 square pyramids,  an edgeedge with one O(1)Li5W octahedra, edges with two equivalent O(2)Li5W octahedra, edges with two equivalent O(5)Li5W octahedra,  an edgeedge with one O(4)Li2W3 square pyramid, and  an edgeedge with one O(3)Li3W2 square pyramid. The corner-sharing octahedral tilt angles range from 14-81°. In the seventh O site, O(7) is bonded in a 6-coordinate geometry to one Li(1), one Li(3), one Li(4), one Li(5), one W(1), and one W(2) atom.