Li4TeO5 is Caswellsilverite-like structured and 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(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Te(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Te(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. 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 two equivalent Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with two equivalent Te(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Te(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Te(1)O6 octahedra, corners with three equivalent Li(5)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-17°. In the fifth Li site, Li(5) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-17°. Te(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form TeO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Te(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(4), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(2)Li5Te octahedra,  an edgeedge with one O(1)Li5Te octahedra, edges with two equivalent O(2)Li5Te octahedra, edges with two equivalent O(5)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(3)Li4Te2 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(5), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(1)Li5Te octahedra,  an edgeedge with one O(2)Li5Te octahedra, edges with two equivalent O(3)Li4Te2 octahedra, edges with two equivalent O(1)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(5)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the third O site, O(3) is bonded to one Li(1), one Li(3), two equivalent Li(4), and two equivalent Te(1) atoms to form OLi4Te2 octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra, corners with two equivalent O(5)Li5Te octahedra,  an edgeedge with one O(5)Li5Te octahedra, edges with two equivalent O(3)Li4Te2 octahedra, edges with two equivalent O(2)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(1)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(4)Li5Te octahedra, edges with three equivalent O(3)Li4Te2 octahedra, edges with three equivalent O(1)Li5Te octahedra, edges with three equivalent O(2)Li5Te octahedra, and edges with three equivalent O(5)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(5), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(3)Li4Te2 octahedra,  an edgeedge with one O(3)Li4Te2 octahedra, edges with two equivalent O(1)Li5Te octahedra, edges with two equivalent O(5)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(2)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-14°.
Li4TeO5 is Caswellsilverite-like structured and 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(1), one O(2), one O(3), one O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with three equivalent Te(1)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Te(1)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-11°. The Li(1)-O(1) bond length is 2.13 Å. The Li(1)-O(2) bond length is 2.09 Å. The Li(1)-O(3) bond length is 2.39 Å. The Li(1)-O(4) bond length is 2.15 Å. There is one shorter (2.04 Å) and one longer (2.06 Å) Li(1)-O(5) bond length. 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 two equivalent Li(3)O6 octahedra, corners with two equivalent Li(5)O6 octahedra, corners with two equivalent Te(1)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with two equivalent Te(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-8°. Both Li(2)-O(2) bond lengths are 2.33 Å. Both Li(2)-O(4) bond lengths are 2.04 Å. Both Li(2)-O(5) bond lengths are 2.05 Å. In the third Li site, Li(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with four equivalent Li(4)O6 octahedra, and edges with four equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-10°. Both Li(3)-O(1) bond lengths are 2.15 Å. Both Li(3)-O(3) bond lengths are 2.04 Å. Both Li(3)-O(4) bond lengths are 2.12 Å. In the fourth Li site, Li(4) is bonded to one O(2), one O(4), two equivalent O(1), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Li(3)O6 octahedra, corners with two equivalent Te(1)O6 octahedra, corners with three equivalent Li(5)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(5)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-17°. The Li(4)-O(2) bond length is 2.07 Å. The Li(4)-O(4) bond length is 2.01 Å. There is one shorter (2.02 Å) and one longer (2.09 Å) Li(4)-O(1) bond length. There is one shorter (2.22 Å) and one longer (2.40 Å) Li(4)-O(3) bond length. In the fifth Li site, Li(5) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(5) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Li(4)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(5)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Te(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-17°. The Li(5)-O(1) bond length is 2.11 Å. The Li(5)-O(4) bond length is 2.08 Å. There is one shorter (2.05 Å) and one longer (2.12 Å) Li(5)-O(2) bond length. There is one shorter (2.05 Å) and one longer (2.30 Å) Li(5)-O(5) bond length. Te(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form TeO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with three equivalent Li(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Te(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent Li(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-10°. The Te(1)-O(1) bond length is 1.90 Å. The Te(1)-O(2) bond length is 1.88 Å. The Te(1)-O(4) bond length is 1.90 Å. The Te(1)-O(5) bond length is 1.89 Å. There is one shorter (2.02 Å) and one longer (2.03 Å) Te(1)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one Li(5), two equivalent Li(4), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(2)Li5Te octahedra,  an edgeedge with one O(1)Li5Te octahedra, edges with two equivalent O(2)Li5Te octahedra, edges with two equivalent O(5)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(3)Li4Te2 octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), two equivalent Li(5), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(1)Li5Te octahedra,  an edgeedge with one O(2)Li5Te octahedra, edges with two equivalent O(3)Li4Te2 octahedra, edges with two equivalent O(1)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(5)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-18°. In the third O site, O(3) is bonded to one Li(1), one Li(3), two equivalent Li(4), and two equivalent Te(1) atoms to form OLi4Te2 octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra, corners with two equivalent O(5)Li5Te octahedra,  an edgeedge with one O(5)Li5Te octahedra, edges with two equivalent O(3)Li4Te2 octahedra, edges with two equivalent O(2)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(1)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one Li(5), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(3)Li4Te2 octahedra,  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(4)Li5Te octahedra, edges with three equivalent O(3)Li4Te2 octahedra, edges with three equivalent O(1)Li5Te octahedra, edges with three equivalent O(2)Li5Te octahedra, and edges with three equivalent O(5)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-13°. In the fifth O site, O(5) is bonded to one Li(2), two equivalent Li(1), two equivalent Li(5), and one Te(1) atom to form OLi5Te octahedra that share  a cornercorner with one O(1)Li5Te octahedra,  a cornercorner with one O(2)Li5Te octahedra,  a cornercorner with one O(4)Li5Te octahedra,  a cornercorner with one O(5)Li5Te octahedra, corners with two equivalent O(3)Li4Te2 octahedra,  an edgeedge with one O(3)Li4Te2 octahedra, edges with two equivalent O(1)Li5Te octahedra, edges with two equivalent O(5)Li5Te octahedra, edges with three equivalent O(4)Li5Te octahedra, and edges with four equivalent O(2)Li5Te octahedra. The corner-sharing octahedral tilt angles range from 0-14°.