LiNa3(MoO4)2 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(3), one O(6), one O(8), and two equivalent O(1) atoms. In the second Na site, Na(2) is bonded to one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Mo(2)O4 tetrahedra, corners with two equivalent Mo(1)O4 tetrahedra, corners with two equivalent Na(2)O5 trigonal bipyramids, and  an edgeedge with one Mo(2)O4 tetrahedra. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom. Li(1) is bonded in a distorted trigonal planar geometry to one O(4), one O(7), and one O(8) atom. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form MoO4 tetrahedra that share corners with two equivalent Na(2)O5 trigonal bipyramids. In the second Mo site, Mo(2) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form MoO4 tetrahedra that share  a cornercorner with one Na(2)O5 trigonal bipyramid and  an edgeedge with one Na(2)O5 trigonal bipyramid. There are eight inequivalent O sites. In the first O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one Mo(1) atom. In the second O site, O(6) is bonded to one Na(1), one Na(2), one Na(3), and one Mo(1) atom to form a mixture of distorted edge and corner-sharing ONa3Mo tetrahedra. In the third O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Li(1), and one Mo(2) atom. In the fourth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Li(1), and one Mo(1) atom. In the fifth O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(3), two equivalent Na(1), and one Mo(2) atom. In the sixth O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(3), two equivalent Na(2), and one Mo(2) atom. In the seventh O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one Mo(2) atom to form a mixture of distorted edge and corner-sharing ONa3Mo trigonal pyramids. In the eighth O site, O(4) is bonded in a distorted T-shaped geometry to one Na(2), one Li(1), and one Mo(1) atom.
LiNa3(MoO4)2 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(3), one O(6), one O(8), and two equivalent O(1) atoms. The Na(1)-O(3) bond length is 2.66 Å. The Na(1)-O(6) bond length is 2.44 Å. The Na(1)-O(8) bond length is 2.36 Å. There is one shorter (2.44 Å) and one longer (2.67 Å) Na(1)-O(1) bond length. In the second Na site, Na(2) is bonded to one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Mo(2)O4 tetrahedra, corners with two equivalent Mo(1)O4 tetrahedra, corners with two equivalent Na(2)O5 trigonal bipyramids, and  an edgeedge with one Mo(2)O4 tetrahedra. The Na(2)-O(3) bond length is 2.51 Å. The Na(2)-O(4) bond length is 2.41 Å. The Na(2)-O(6) bond length is 2.52 Å. There is one shorter (2.43 Å) and one longer (2.70 Å) Na(2)-O(2) bond length. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(6), and one O(7) atom. The Na(3)-O(1) bond length is 2.63 Å. The Na(3)-O(2) bond length is 2.57 Å. The Na(3)-O(3) bond length is 2.45 Å. The Na(3)-O(5) bond length is 2.28 Å. The Na(3)-O(6) bond length is 2.37 Å. The Na(3)-O(7) bond length is 2.68 Å. Li(1) is bonded in a distorted trigonal planar geometry to one O(4), one O(7), and one O(8) atom. The Li(1)-O(4) bond length is 2.05 Å. The Li(1)-O(7) bond length is 1.93 Å. The Li(1)-O(8) bond length is 2.00 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(4), one O(5), one O(6), and one O(8) atom to form MoO4 tetrahedra that share corners with two equivalent Na(2)O5 trigonal bipyramids. The Mo(1)-O(4) bond length is 1.81 Å. The Mo(1)-O(5) bond length is 1.77 Å. The Mo(1)-O(6) bond length is 1.81 Å. The Mo(1)-O(8) bond length is 1.82 Å. In the second Mo site, Mo(2) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form MoO4 tetrahedra that share  a cornercorner with one Na(2)O5 trigonal bipyramid and  an edgeedge with one Na(2)O5 trigonal bipyramid. The Mo(2)-O(1) bond length is 1.80 Å. The Mo(2)-O(2) bond length is 1.80 Å. The Mo(2)-O(3) bond length is 1.80 Å. The Mo(2)-O(7) bond length is 1.80 Å. There are eight inequivalent O sites. In the first O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one Mo(1) atom. In the second O site, O(6) is bonded to one Na(1), one Na(2), one Na(3), and one Mo(1) atom to form a mixture of distorted edge and corner-sharing ONa3Mo tetrahedra. In the third O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Li(1), and one Mo(2) atom. In the fourth O site, O(8) is bonded in a distorted trigonal planar geometry to one Na(1), one Li(1), and one Mo(1) atom. In the fifth O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(3), two equivalent Na(1), and one Mo(2) atom. In the sixth O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(3), two equivalent Na(2), and one Mo(2) atom. In the seventh O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), and one Mo(2) atom to form a mixture of distorted edge and corner-sharing ONa3Mo trigonal pyramids. In the eighth O site, O(4) is bonded in a distorted T-shaped geometry to one Na(2), one Li(1), and one Mo(1) atom.