Na5Cu3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2), two equivalent O(5), and four equivalent O(8) atoms to form distorted NaO8 hexagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Cu(2)O5 square pyramids, and edges with two equivalent P(2)O4 tetrahedra. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(7), and two equivalent O(6) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(3), one O(6), one O(8), and three equivalent O(4) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(5), one O(6), and one O(7) atom to form CuO5 square pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid and corners with two equivalent Cu(2)O5 square pyramids. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid, corners with three equivalent Cu(2)O5 square pyramids, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), one Cu(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Cu(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(2), one Cu(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Cu(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Na(3), two equivalent Na(1), and one P(2) atom.
Na5Cu3(PO4)4 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(2), two equivalent O(5), and four equivalent O(8) atoms to form distorted NaO8 hexagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Na(1)O8 hexagonal bipyramids, edges with two equivalent Cu(2)O5 square pyramids, and edges with two equivalent P(2)O4 tetrahedra. Both Na(1)-O(2) bond lengths are 2.41 Å. Both Na(1)-O(5) bond lengths are 2.54 Å. There are two shorter (2.84 Å) and two longer (2.92 Å) Na(1)-O(8) bond lengths. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(3), one O(4), one O(5), one O(7), and two equivalent O(6) atoms. The Na(2)-O(1) bond length is 2.74 Å. The Na(2)-O(3) bond length is 2.50 Å. The Na(2)-O(4) bond length is 2.46 Å. The Na(2)-O(5) bond length is 2.36 Å. The Na(2)-O(7) bond length is 2.28 Å. There is one shorter (2.49 Å) and one longer (2.83 Å) Na(2)-O(6) bond length. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(3), one O(6), one O(8), and three equivalent O(4) atoms. The Na(3)-O(3) bond length is 2.39 Å. The Na(3)-O(6) bond length is 2.52 Å. The Na(3)-O(8) bond length is 2.24 Å. There are a spread of Na(3)-O(4) bond distances ranging from 2.34-2.80 Å. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a square co-planar geometry to two equivalent O(1) and two equivalent O(3) atoms. Both Cu(1)-O(1) bond lengths are 2.07 Å. Both Cu(1)-O(3) bond lengths are 1.94 Å. In the second Cu site, Cu(2) is bonded to one O(1), one O(2), one O(5), one O(6), and one O(7) atom to form CuO5 square pyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The Cu(2)-O(1) bond length is 2.06 Å. The Cu(2)-O(2) bond length is 1.96 Å. The Cu(2)-O(5) bond length is 1.94 Å. The Cu(2)-O(6) bond length is 1.93 Å. The Cu(2)-O(7) bond length is 2.25 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid and corners with two equivalent Cu(2)O5 square pyramids. The P(1)-O(1) bond length is 1.60 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid, corners with three equivalent Cu(2)O5 square pyramids, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The P(2)-O(5) bond length is 1.59 Å. The P(2)-O(6) bond length is 1.60 Å. The P(2)-O(7) bond length is 1.52 Å. The P(2)-O(8) bond length is 1.53 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), one Cu(2), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Na(1), one Cu(2), and one P(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), three equivalent Na(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Cu(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(3), two equivalent Na(2), one Cu(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Cu(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Na(3), two equivalent Na(1), and one P(2) atom.