LiBa3Ti3O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a distorted q6 geometry to one O(5), two equivalent O(2), two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(5), two equivalent O(2), and two equivalent O(3) atoms to form TiO5 square pyramids that share corners with three equivalent Ti(3)O6 octahedra and corners with two equivalent Ti(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 4-7°. In the second Ti site, Ti(2) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form TiO5 square pyramids that share corners with three equivalent Ti(3)O6 octahedra and corners with two equivalent Ti(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-5°. In the third Ti site, Ti(3) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form corner-sharing TiO6 octahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Ba(2), one Ba(3), two equivalent Ba(1), one Ti(2), and one Ti(3) atom to form a mixture of distorted corner and face-sharing OBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 1-63°. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Ba(1), one Ba(3), one Ti(1), and one Ti(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ba(1), one Ba(2), one Ti(1), and one Ti(3) atom. In the fourth O site, O(4) is bonded to one Ba(2), one Ba(3), two equivalent Ba(1), one Ti(2), and one Ti(3) atom to form a mixture of distorted corner and face-sharing OBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 1-63°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), one Ti(1), and one Ti(3) atom.
LiBa3Ti3O8 crystallizes in the monoclinic Cm space group. Li(1) is bonded in a rectangular see-saw-like geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Li(1)-O(2) bond lengths are 1.96 Å. Both Li(1)-O(3) bond lengths are 1.97 Å. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a distorted q6 geometry to one O(5), two equivalent O(2), two equivalent O(3), two equivalent O(4), and four equivalent O(1) atoms. The Ba(1)-O(5) bond length is 2.95 Å. Both Ba(1)-O(2) bond lengths are 3.00 Å. Both Ba(1)-O(3) bond lengths are 2.98 Å. Both Ba(1)-O(4) bond lengths are 2.83 Å. There are two shorter (2.97 Å) and two longer (2.99 Å) Ba(1)-O(1) bond lengths. In the second Ba site, Ba(2) is bonded in a 7-coordinate geometry to one O(4), two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms. The Ba(2)-O(4) bond length is 2.96 Å. Both Ba(2)-O(1) bond lengths are 2.71 Å. Both Ba(2)-O(3) bond lengths are 2.75 Å. Both Ba(2)-O(5) bond lengths are 2.86 Å. In the third Ba site, Ba(3) is bonded in a 6-coordinate geometry to one O(4), one O(5), two equivalent O(1), and two equivalent O(2) atoms. The Ba(3)-O(4) bond length is 2.81 Å. The Ba(3)-O(5) bond length is 2.87 Å. Both Ba(3)-O(1) bond lengths are 2.69 Å. Both Ba(3)-O(2) bond lengths are 2.75 Å. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to one O(5), two equivalent O(2), and two equivalent O(3) atoms to form TiO5 square pyramids that share corners with three equivalent Ti(3)O6 octahedra and corners with two equivalent Ti(2)O5 square pyramids. The corner-sharing octahedral tilt angles range from 4-7°. The Ti(1)-O(5) bond length is 1.93 Å. Both Ti(1)-O(2) bond lengths are 2.05 Å. Both Ti(1)-O(3) bond lengths are 1.97 Å. In the second Ti site, Ti(2) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form TiO5 square pyramids that share corners with three equivalent Ti(3)O6 octahedra and corners with two equivalent Ti(1)O5 square pyramids. The corner-sharing octahedral tilt angles range from 1-5°. The Ti(2)-O(4) bond length is 1.95 Å. Both Ti(2)-O(1) bond lengths are 2.00 Å. Both Ti(2)-O(2) bond lengths are 2.03 Å. In the third Ti site, Ti(3) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form corner-sharing TiO6 octahedra. The Ti(3)-O(4) bond length is 2.13 Å. The Ti(3)-O(5) bond length is 2.22 Å. Both Ti(3)-O(1) bond lengths are 2.06 Å. Both Ti(3)-O(3) bond lengths are 2.04 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Ba(2), one Ba(3), two equivalent Ba(1), one Ti(2), and one Ti(3) atom to form a mixture of distorted corner and face-sharing OBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 1-63°. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Ba(1), one Ba(3), one Ti(1), and one Ti(2) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ba(1), one Ba(2), one Ti(1), and one Ti(3) atom. In the fourth O site, O(4) is bonded to one Ba(2), one Ba(3), two equivalent Ba(1), one Ti(2), and one Ti(3) atom to form a mixture of distorted corner and face-sharing OBa4Ti2 octahedra. The corner-sharing octahedral tilt angles range from 1-63°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Ba(1), one Ba(3), two equivalent Ba(2), one Ti(1), and one Ti(3) atom.