NaCu(PO3)4 crystallizes in the monoclinic Cc space group. Na(1) is bonded to one O(10), one O(12), one O(2), one O(7), and one O(9) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Cu(1) is bonded in a 4-coordinate geometry to one O(12), one O(2), one O(5), and one O(6) 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 corner-sharing PO4 tetrahedra. 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, and corners with two equivalent Na(1)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, and  a cornercorner with one Na(1)O5 trigonal bipyramid. 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(1)O5 trigonal bipyramids. There are twelve inequivalent O sites. In the first O site, O(8) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the second O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one P(3) atom. In the third O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one P(4) atom. In the fourth O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the fifth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one P(4) atom. In the sixth O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the seventh O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one P(2) atom. In the eighth O site, O(3) is bonded in a distorted single-bond geometry to one P(1) atom. In the ninth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the tenth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the eleventh O site, O(6) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(3) atom. In the twelfth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one P(2) atom.
NaCu(PO3)4 crystallizes in the monoclinic Cc space group. Na(1) is bonded to one O(10), one O(12), one O(2), one O(7), and one O(9) atom to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Na(1)-O(10) bond length is 2.40 Å. The Na(1)-O(12) bond length is 2.65 Å. The Na(1)-O(2) bond length is 2.39 Å. The Na(1)-O(7) bond length is 2.22 Å. The Na(1)-O(9) bond length is 2.31 Å. Cu(1) is bonded in a 4-coordinate geometry to one O(12), one O(2), one O(5), and one O(6) atom. The Cu(1)-O(12) bond length is 1.88 Å. The Cu(1)-O(2) bond length is 1.90 Å. The Cu(1)-O(5) bond length is 1.87 Å. The Cu(1)-O(6) bond length is 1.86 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 corner-sharing PO4 tetrahedra. The P(1)-O(1) bond length is 1.62 Å. The P(1)-O(3) bond length is 1.48 Å. The P(1)-O(4) bond length is 1.61 Å. The P(1)-O(5) bond length is 1.54 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, and corners with two equivalent Na(1)O5 trigonal bipyramids. The P(2)-O(2) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.61 Å. The P(2)-O(7) bond length is 1.47 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, and  a cornercorner with one Na(1)O5 trigonal bipyramid. The P(3)-O(11) bond length is 1.62 Å. The P(3)-O(6) bond length is 1.54 Å. The P(3)-O(8) bond length is 1.62 Å. The P(3)-O(9) bond length is 1.47 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(1)O5 trigonal bipyramids. The P(4)-O(1) bond length is 1.60 Å. The P(4)-O(10) bond length is 1.48 Å. The P(4)-O(11) bond length is 1.60 Å. The P(4)-O(12) bond length is 1.55 Å. There are twelve inequivalent O sites. In the first O site, O(8) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the second O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one P(3) atom. In the third O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one P(4) atom. In the fourth O site, O(11) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the fifth O site, O(12) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one P(4) atom. In the sixth O site, O(1) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the seventh O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Cu(1), and one P(2) atom. In the eighth O site, O(3) is bonded in a distorted single-bond geometry to one P(1) atom. In the ninth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the tenth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Cu(1) and one P(1) atom. In the eleventh O site, O(6) is bonded in a bent 120 degrees geometry to one Cu(1) and one P(3) atom. In the twelfth O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one P(2) atom.