Li4La5Ti6Nb2O26 crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(7) atoms. There are three inequivalent La sites. In the first La site, La(1) is bonded to two equivalent O(5), two equivalent O(6), and eight equivalent O(3) atoms to form LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with eight equivalent La(3)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(3)O6 octahedra. In the second La site, La(2) is bonded to two equivalent O(1), two equivalent O(8), four equivalent O(3), and four equivalent O(4) atoms to form LaO12 cuboctahedra that share corners with four equivalent La(2)O12 cuboctahedra,  a faceface with one La(1)O12 cuboctahedra, faces with four equivalent La(3)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Nb(1)O6 octahedra. In the third La site, La(3) is bonded to two equivalent O(1), two equivalent O(8), four equivalent O(3), and four equivalent O(4) atoms to form LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with four equivalent La(3)O12 cuboctahedra, faces with four equivalent La(2)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Nb(1)O6 octahedra. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(5), and four equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra, corners with four equivalent Ti(3)O6 octahedra, faces with two equivalent La(1)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-9°. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), and four equivalent O(4) atoms to form distorted TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-19°. In the third Ti site, Ti(3) is bonded to one O(6), one O(8), and four equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Ti(3)O6 octahedra,  a cornercorner with one Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, faces with two equivalent La(1)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-9°. Nb(1) is bonded to one O(7), one O(8), and four equivalent O(4) atoms to form distorted NbO6 octahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-19°. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent La(2), two equivalent La(3), one Ti(1), and one Ti(2) atom to form distorted OLa4Ti2 octahedra that share corners with four equivalent O(1)La4Ti2 octahedra, corners with eight equivalent O(3)La3Ti2 square pyramids,  a cornercorner with one O(2)Li4Ti trigonal bipyramid, edges with four equivalent O(8)La4TiNb octahedra, and faces with four equivalent O(3)La3Ti2 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the second O site, O(2) is bonded to four equivalent Li(1) and one Ti(2) atom to form distorted OLi4Ti trigonal bipyramids that share  a cornercorner with one O(1)La4Ti2 octahedra, corners with four equivalent O(7)Li4Nb square pyramids, edges with two equivalent O(7)Li4Nb square pyramids, and edges with two equivalent O(2)Li4Ti trigonal bipyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one La(1), one La(2), one La(3), one Ti(1), and one Ti(3) atom to form distorted OLa3Ti2 square pyramids that share corners with two equivalent O(1)La4Ti2 octahedra, corners with two equivalent O(8)La4TiNb octahedra, corners with seven equivalent O(3)La3Ti2 square pyramids, edges with three equivalent O(3)La3Ti2 square pyramids,  a faceface with one O(1)La4Ti2 octahedra,  a faceface with one O(8)La4TiNb octahedra, and faces with two equivalent O(3)La3Ti2 square pyramids. The corner-sharing octahedral tilt angles range from 59-61°. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one La(2), one La(3), one Ti(2), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to two equivalent La(1) and two equivalent Ti(1) atoms. In the sixth O site, O(6) is bonded in a distorted linear geometry to two equivalent La(1) and two equivalent Ti(3) atoms. In the seventh O site, O(7) is bonded to four equivalent Li(1) and one Nb(1) atom to form distorted OLi4Nb square pyramids that share  a cornercorner with one O(8)La4TiNb octahedra, corners with four equivalent O(2)Li4Ti trigonal bipyramids, edges with two equivalent O(7)Li4Nb square pyramids, and edges with two equivalent O(2)Li4Ti trigonal bipyramids. The corner-sharing octahedra are not tilted. In the eighth O site, O(8) is bonded to two equivalent La(2), two equivalent La(3), one Ti(3), and one Nb(1) atom to form distorted OLa4TiNb octahedra that share corners with four equivalent O(8)La4TiNb octahedra,  a cornercorner with one O(7)Li4Nb square pyramid, corners with eight equivalent O(3)La3Ti2 square pyramids, edges with four equivalent O(1)La4Ti2 octahedra, and faces with four equivalent O(3)La3Ti2 square pyramids. The corner-sharing octahedral tilt angles are 2°.
Li4La5Ti6Nb2O26 crystallizes in the orthorhombic Cmmm space group. Li(1) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(7) atoms. Both Li(1)-O(2) bond lengths are 2.00 Å. Both Li(1)-O(7) bond lengths are 2.06 Å. There are three inequivalent La sites. In the first La site, La(1) is bonded to two equivalent O(5), two equivalent O(6), and eight equivalent O(3) atoms to form LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with eight equivalent La(3)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, faces with four equivalent Ti(1)O6 octahedra, and faces with four equivalent Ti(3)O6 octahedra. Both La(1)-O(5) bond lengths are 2.78 Å. Both La(1)-O(6) bond lengths are 2.79 Å. All La(1)-O(3) bond lengths are 2.81 Å. In the second La site, La(2) is bonded to two equivalent O(1), two equivalent O(8), four equivalent O(3), and four equivalent O(4) atoms to form LaO12 cuboctahedra that share corners with four equivalent La(2)O12 cuboctahedra,  a faceface with one La(1)O12 cuboctahedra, faces with four equivalent La(3)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Nb(1)O6 octahedra. Both La(2)-O(1) bond lengths are 2.79 Å. Both La(2)-O(8) bond lengths are 2.79 Å. All La(2)-O(3) bond lengths are 2.68 Å. All La(2)-O(4) bond lengths are 2.66 Å. In the third La site, La(3) is bonded to two equivalent O(1), two equivalent O(8), four equivalent O(3), and four equivalent O(4) atoms to form LaO12 cuboctahedra that share corners with four equivalent La(1)O12 cuboctahedra, corners with four equivalent La(3)O12 cuboctahedra, faces with four equivalent La(2)O12 cuboctahedra, faces with two equivalent Ti(1)O6 octahedra, faces with two equivalent Ti(2)O6 octahedra, faces with two equivalent Ti(3)O6 octahedra, and faces with two equivalent Nb(1)O6 octahedra. Both La(3)-O(1) bond lengths are 2.79 Å. Both La(3)-O(8) bond lengths are 2.78 Å. All La(3)-O(3) bond lengths are 2.78 Å. All La(3)-O(4) bond lengths are 2.66 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(1), one O(5), and four equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra, corners with four equivalent Ti(3)O6 octahedra, faces with two equivalent La(1)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Ti(1)-O(1) bond length is 1.97 Å. The Ti(1)-O(5) bond length is 1.95 Å. All Ti(1)-O(3) bond lengths are 1.98 Å. In the second Ti site, Ti(2) is bonded to one O(1), one O(2), and four equivalent O(4) atoms to form distorted TiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with four equivalent Nb(1)O6 octahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-19°. The Ti(2)-O(1) bond length is 2.16 Å. The Ti(2)-O(2) bond length is 1.80 Å. All Ti(2)-O(4) bond lengths are 1.98 Å. In the third Ti site, Ti(3) is bonded to one O(6), one O(8), and four equivalent O(3) atoms to form TiO6 octahedra that share  a cornercorner with one Ti(3)O6 octahedra,  a cornercorner with one Nb(1)O6 octahedra, corners with four equivalent Ti(1)O6 octahedra, faces with two equivalent La(1)O12 cuboctahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-9°. The Ti(3)-O(6) bond length is 1.93 Å. The Ti(3)-O(8) bond length is 1.99 Å. All Ti(3)-O(3) bond lengths are 1.97 Å. Nb(1) is bonded to one O(7), one O(8), and four equivalent O(4) atoms to form distorted NbO6 octahedra that share  a cornercorner with one Ti(3)O6 octahedra, corners with four equivalent Ti(2)O6 octahedra, faces with two equivalent La(2)O12 cuboctahedra, and faces with two equivalent La(3)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 0-19°. The Nb(1)-O(7) bond length is 1.87 Å. The Nb(1)-O(8) bond length is 2.18 Å. All Nb(1)-O(4) bond lengths are 2.01 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded to two equivalent La(2), two equivalent La(3), one Ti(1), and one Ti(2) atom to form distorted OLa4Ti2 octahedra that share corners with four equivalent O(1)La4Ti2 octahedra, corners with eight equivalent O(3)La3Ti2 square pyramids,  a cornercorner with one O(2)Li4Ti trigonal bipyramid, edges with four equivalent O(8)La4TiNb octahedra, and faces with four equivalent O(3)La3Ti2 square pyramids. The corner-sharing octahedral tilt angles are 2°. In the second O site, O(2) is bonded to four equivalent Li(1) and one Ti(2) atom to form distorted OLi4Ti trigonal bipyramids that share  a cornercorner with one O(1)La4Ti2 octahedra, corners with four equivalent O(7)Li4Nb square pyramids, edges with two equivalent O(7)Li4Nb square pyramids, and edges with two equivalent O(2)Li4Ti trigonal bipyramids. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to one La(1), one La(2), one La(3), one Ti(1), and one Ti(3) atom to form distorted OLa3Ti2 square pyramids that share corners with two equivalent O(1)La4Ti2 octahedra, corners with two equivalent O(8)La4TiNb octahedra, corners with seven equivalent O(3)La3Ti2 square pyramids, edges with three equivalent O(3)La3Ti2 square pyramids,  a faceface with one O(1)La4Ti2 octahedra,  a faceface with one O(8)La4TiNb octahedra, and faces with two equivalent O(3)La3Ti2 square pyramids. The corner-sharing octahedral tilt angles range from 59-61°. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one La(2), one La(3), one Ti(2), and one Nb(1) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to two equivalent La(1) and two equivalent Ti(1) atoms. In the sixth O site, O(6) is bonded in a distorted linear geometry to two equivalent La(1) and two equivalent Ti(3) atoms. In the seventh O site, O(7) is bonded to four equivalent Li(1) and one Nb(1) atom to form distorted OLi4Nb square pyramids that share  a cornercorner with one O(8)La4TiNb octahedra, corners with four equivalent O(2)Li4Ti trigonal bipyramids, edges with two equivalent O(7)Li4Nb square pyramids, and edges with two equivalent O(2)Li4Ti trigonal bipyramids. The corner-sharing octahedra are not tilted. In the eighth O site, O(8) is bonded to two equivalent La(2), two equivalent La(3), one Ti(3), and one Nb(1) atom to form distorted OLa4TiNb octahedra that share corners with four equivalent O(8)La4TiNb octahedra,  a cornercorner with one O(7)Li4Nb square pyramid, corners with eight equivalent O(3)La3Ti2 square pyramids, edges with four equivalent O(1)La4Ti2 octahedra, and faces with four equivalent O(3)La3Ti2 square pyramids. The corner-sharing octahedral tilt angles are 2°.