Na2LiCu(PO3)4 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(5), one O(6), one O(7), and one O(9) atom to form NaO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Na(2)O5 trigonal bipyramid. In the second Na site, Na(2) is bonded to one O(10), one O(12), one O(2), one O(7), and one O(9) atom to form NaO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Na(1)O5 trigonal bipyramid. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(5), and one O(6) atom. Cu(1) is bonded in a 3-coordinate geometry to one O(12), one O(2), and one O(3) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent Na(1)O5 trigonal bipyramids. In the second P site, P(2) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, and corners with two equivalent Na(2)O5 trigonal bipyramids. In the third P site, P(3) is bonded to one O(11), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and corners with two equivalent Na(1)O5 trigonal bipyramids. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(11), and one O(12) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Na(2)O5 trigonal bipyramids. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one P(1), and one P(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Li(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one P(4) atom.
Na2LiCu(PO3)4 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(5), one O(6), one O(7), and one O(9) atom to form NaO5 trigonal bipyramids that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one Na(2)O5 trigonal bipyramid. The Na(1)-O(3) bond length is 2.52 Å. The Na(1)-O(5) bond length is 2.46 Å. The Na(1)-O(6) bond length is 2.35 Å. The Na(1)-O(7) bond length is 2.48 Å. The Na(1)-O(9) bond length is 2.30 Å. In the second Na site, Na(2) is bonded to one O(10), one O(12), one O(2), one O(7), and one O(9) atom to form NaO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one Na(1)O5 trigonal bipyramid. The Na(2)-O(10) bond length is 2.45 Å. The Na(2)-O(12) bond length is 2.35 Å. The Na(2)-O(2) bond length is 2.36 Å. The Na(2)-O(7) bond length is 2.31 Å. The Na(2)-O(9) bond length is 2.52 Å. Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(10), one O(5), and one O(6) atom. The Li(1)-O(1) bond length is 2.32 Å. The Li(1)-O(10) bond length is 2.03 Å. The Li(1)-O(5) bond length is 1.91 Å. The Li(1)-O(6) bond length is 1.91 Å. Cu(1) is bonded in a 3-coordinate geometry to one O(12), one O(2), and one O(3) atom. The Cu(1)-O(12) bond length is 2.19 Å. The Cu(1)-O(2) bond length is 1.97 Å. The Cu(1)-O(3) bond length is 1.95 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent Na(1)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.62 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(4) bond length is 1.61 Å. The P(1)-O(5) bond length is 1.49 Å. In the second P site, P(2) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, and corners with two equivalent Na(2)O5 trigonal bipyramids. The P(2)-O(2) bond length is 1.52 Å. The P(2)-O(4) bond length is 1.62 Å. The P(2)-O(7) bond length is 1.49 Å. The P(2)-O(8) bond length is 1.62 Å. In the third P site, P(3) is bonded to one O(11), one O(6), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  a cornercorner with one Na(2)O5 trigonal bipyramid, and corners with two equivalent Na(1)O5 trigonal bipyramids. The P(3)-O(11) bond length is 1.62 Å. The P(3)-O(6) bond length is 1.51 Å. The P(3)-O(8) bond length is 1.63 Å. The P(3)-O(9) bond length is 1.49 Å. In the fourth P site, P(4) is bonded to one O(1), one O(10), one O(11), and one O(12) atom to form PO4 tetrahedra that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent Na(2)O5 trigonal bipyramids. The P(4)-O(1) bond length is 1.65 Å. The P(4)-O(10) bond length is 1.50 Å. The P(4)-O(11) bond length is 1.61 Å. The P(4)-O(12) bond length is 1.50 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one P(1), and one P(4) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one Li(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Li(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one P(4) atom.