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 in a 4-coordinate geometry to two equivalent O(5) and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Cu(1), one O(1), one O(3), one O(5), one O(6), and one O(8) atom. In the third Na site, Na(3) is bonded in a 2-coordinate geometry to one O(7), one O(8), and two equivalent O(4) atoms. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to two equivalent Na(2), two equivalent O(1), and two equivalent O(3) atoms. In the second Cu site, Cu(2) is bonded in a 2-coordinate geometry to one O(2), one O(6), and one O(7) atom. There are two inequivalent P sites. In the first P site, P(1) is bonded in a 3-coordinate geometry to one O(2), one O(3), and one O(4) atom. In the second P site, P(2) is bonded in a 2-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Na(2) and one Cu(1) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one Cu(2) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(3) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Na(2), one Cu(2), one P(2), and one O(8) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Cu(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one P(2), one O(6), and one O(8) 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 in a 4-coordinate geometry to two equivalent O(5) and two equivalent O(8) atoms. Both Na(1)-O(5) bond lengths are 2.50 Å. Both Na(1)-O(8) bond lengths are 2.45 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one Cu(1), one O(1), one O(3), one O(5), one O(6), and one O(8) atom. The Na(2)-Cu(1) bond length is 2.22 Å. The Na(2)-O(1) bond length is 2.56 Å. The Na(2)-O(3) bond length is 2.20 Å. The Na(2)-O(5) bond length is 2.77 Å. The Na(2)-O(6) bond length is 2.41 Å. The Na(2)-O(8) bond length is 2.58 Å. In the third Na site, Na(3) is bonded in a 2-coordinate geometry to one O(7), one O(8), and two equivalent O(4) atoms. The Na(3)-O(7) bond length is 2.98 Å. The Na(3)-O(8) bond length is 2.99 Å. There is one shorter (1.98 Å) and one longer (2.37 Å) Na(3)-O(4) bond length. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 6-coordinate geometry to two equivalent Na(2), two equivalent O(1), and two equivalent O(3) atoms. Both Cu(1)-O(1) bond lengths are 1.70 Å. Both Cu(1)-O(3) bond lengths are 1.93 Å. In the second Cu site, Cu(2) is bonded in a 2-coordinate geometry to one O(2), one O(6), and one O(7) atom. The Cu(2)-O(2) bond length is 1.54 Å. The Cu(2)-O(6) bond length is 1.67 Å. The Cu(2)-O(7) bond length is 2.50 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded in a 3-coordinate geometry to one O(2), one O(3), and one O(4) atom. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(3) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.71 Å. In the second P site, P(2) is bonded in a 2-coordinate geometry to one O(5), one O(6), one O(7), and one O(8) atom. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.27 Å. The P(2)-O(7) bond length is 2.39 Å. The P(2)-O(8) bond length is 2.03 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Na(2) and one Cu(1) atom. In the second O site, O(2) is bonded in an L-shaped geometry to one Cu(2) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Cu(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to two equivalent Na(3) and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 2-coordinate geometry to one Na(2), one Cu(2), one P(2), and one O(8) atom. The O(6)-O(8) bond length is 1.79 Å. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Cu(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(3), one P(2), one O(6), and one O(8) atom. The O(8)-O(8) bond length is 1.70 Å.