LiBa3(AsO4)2 crystallizes in the trigonal R-3m space group. Li(1) is bonded in a 6-coordinate geometry to six equivalent O(2) atoms. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(1) and nine equivalent O(2) atoms. In the second Ba site, Ba(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted BaO12 cuboctahedra that share edges with six equivalent Ba(2)O12 cuboctahedra and edges with six equivalent As(1)O4 tetrahedra. As(1) is bonded to one O(1) and three equivalent O(2) atoms to form distorted AsO4 tetrahedra that share edges with three equivalent Ba(2)O12 cuboctahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one Ba(1), three equivalent Ba(2), and one As(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Ba(2), three equivalent Ba(1), and one As(1) atom.
LiBa3(AsO4)2 crystallizes in the trigonal R-3m space group. Li(1) is bonded in a 6-coordinate geometry to six equivalent O(2) atoms. All Li(1)-O(2) bond lengths are 2.19 Å. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to one O(1) and nine equivalent O(2) atoms. The Ba(1)-O(1) bond length is 2.57 Å. There are six shorter (3.00 Å) and three longer (3.05 Å) Ba(1)-O(2) bond lengths. In the second Ba site, Ba(2) is bonded to six equivalent O(1) and six equivalent O(2) atoms to form distorted BaO12 cuboctahedra that share edges with six equivalent Ba(2)O12 cuboctahedra and edges with six equivalent As(1)O4 tetrahedra. All Ba(2)-O(1) bond lengths are 3.41 Å. All Ba(2)-O(2) bond lengths are 2.93 Å. As(1) is bonded to one O(1) and three equivalent O(2) atoms to form distorted AsO4 tetrahedra that share edges with three equivalent Ba(2)O12 cuboctahedra. The As(1)-O(1) bond length is 1.75 Å. All As(1)-O(2) bond lengths are 1.80 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a distorted linear geometry to one Ba(1), three equivalent Ba(2), and one As(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(1), one Ba(2), three equivalent Ba(1), and one As(1) atom.