LiNaSO4 crystallizes in the trigonal P31c space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and two equivalent O(6) atoms. Li(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are three inequivalent S sites. In the first S site, S(1) is bonded to one O(2) and three equivalent O(5) atoms to form SO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra. In the second S site, S(2) is bonded to one O(3) and three equivalent O(6) atoms to form SO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra. In the third S site, S(3) is bonded to one O(4) and three equivalent O(1) atoms to form SO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), and one S(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one S(3) atom. In the third O site, O(2) is bonded in a distorted trigonal pyramidal geometry to three equivalent Li(1) and one S(1) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to three equivalent Na(1) and one S(2) atom. In the fifth O site, O(4) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(3) atom. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one S(1) atom.
LiNaSO4 crystallizes in the trigonal P31c space group. Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and two equivalent O(6) atoms. The Na(1)-O(1) bond length is 2.39 Å. The Na(1)-O(3) bond length is 2.53 Å. The Na(1)-O(4) bond length is 2.43 Å. The Na(1)-O(5) bond length is 2.42 Å. There is one shorter (2.47 Å) and one longer (2.78 Å) Na(1)-O(6) bond length. Li(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one S(2)O4 tetrahedra,  a cornercorner with one S(3)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Li(1)-O(1) bond length is 1.94 Å. The Li(1)-O(2) bond length is 2.09 Å. The Li(1)-O(5) bond length is 2.05 Å. The Li(1)-O(6) bond length is 1.96 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded to one O(2) and three equivalent O(5) atoms to form SO4 tetrahedra that share corners with six equivalent Li(1)O4 tetrahedra. The S(1)-O(2) bond length is 1.52 Å. All S(1)-O(5) bond lengths are 1.49 Å. In the second S site, S(2) is bonded to one O(3) and three equivalent O(6) atoms to form SO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra. The S(2)-O(3) bond length is 1.49 Å. All S(2)-O(6) bond lengths are 1.50 Å. In the third S site, S(3) is bonded to one O(4) and three equivalent O(1) atoms to form SO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra. The S(3)-O(4) bond length is 1.49 Å. All S(3)-O(1) bond lengths are 1.49 Å. There are six inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Li(1), and one S(2) atom. In the second O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one S(3) atom. In the third O site, O(2) is bonded in a distorted trigonal pyramidal geometry to three equivalent Li(1) and one S(1) atom. In the fourth O site, O(3) is bonded in a distorted single-bond geometry to three equivalent Na(1) and one S(2) atom. In the fifth O site, O(4) is bonded in a 4-coordinate geometry to three equivalent Na(1) and one S(3) atom. In the sixth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one S(1) atom.