LiCeS2O9 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(7), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one S(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with three equivalent S(2)O4 tetrahedra. Ce(1) is bonded in a 9-coordinate geometry to one O(3), one O(4), one O(6), one O(7), one O(9), two equivalent O(2), and two equivalent O(8) atoms. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra. In the second S site, S(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form SO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra. There are nine inequivalent O sites. In the first O site, O(5) is bonded in a trigonal planar geometry to two equivalent Li(1) and one S(2) atom. In the second O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one S(2) atom. In the third O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Ce(1), and one S(2) atom. In the fourth O site, O(8) is bonded in a distorted single-bond geometry to two equivalent Ce(1) and one S(2) atom. In the fifth O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one S(1) atom. In the sixth O site, O(9) is bonded in a single-bond geometry to one Ce(1) atom. In the seventh O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Ce(1) and one S(1) atom. In the eighth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one S(1) atom. In the ninth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one S(1) atom.
LiCeS2O9 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(7), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one S(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with three equivalent S(2)O4 tetrahedra. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(7) bond length is 2.05 Å. There is one shorter (1.95 Å) and one longer (1.97 Å) Li(1)-O(5) bond length. Ce(1) is bonded in a 9-coordinate geometry to one O(3), one O(4), one O(6), one O(7), one O(9), two equivalent O(2), and two equivalent O(8) atoms. The Ce(1)-O(3) bond length is 2.38 Å. The Ce(1)-O(4) bond length is 2.51 Å. The Ce(1)-O(6) bond length is 2.42 Å. The Ce(1)-O(7) bond length is 2.74 Å. The Ce(1)-O(9) bond length is 2.03 Å. There is one shorter (2.53 Å) and one longer (2.67 Å) Ce(1)-O(2) bond length. There is one shorter (2.53 Å) and one longer (2.82 Å) Ce(1)-O(8) bond length. There are two inequivalent S sites. In the first S site, S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra. The S(1)-O(1) bond length is 1.45 Å. The S(1)-O(2) bond length is 1.52 Å. The S(1)-O(3) bond length is 1.50 Å. The S(1)-O(4) bond length is 1.49 Å. In the second S site, S(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form SO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra. The S(2)-O(5) bond length is 1.48 Å. The S(2)-O(6) bond length is 1.48 Å. The S(2)-O(7) bond length is 1.48 Å. The S(2)-O(8) bond length is 1.51 Å. There are nine inequivalent O sites. In the first O site, O(5) is bonded in a trigonal planar geometry to two equivalent Li(1) and one S(2) atom. In the second O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one S(2) atom. In the third O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Li(1), one Ce(1), and one S(2) atom. In the fourth O site, O(8) is bonded in a distorted single-bond geometry to two equivalent Ce(1) and one S(2) atom. In the fifth O site, O(1) is bonded in a bent 120 degrees geometry to one Li(1) and one S(1) atom. In the sixth O site, O(9) is bonded in a single-bond geometry to one Ce(1) atom. In the seventh O site, O(2) is bonded in a distorted single-bond geometry to two equivalent Ce(1) and one S(1) atom. In the eighth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one S(1) atom. In the ninth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Ce(1) and one S(1) atom.