Na3PO4 is Enargite structured and crystallizes in the monoclinic Pm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form NaO4 tetrahedra that share corners with two equivalent Na(1)O4 tetrahedra, corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(3)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Na site, Na(2) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form NaO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. In the third Na site, Na(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form NaO4 tetrahedra that share corners with two equivalent Na(1)O4 tetrahedra, corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(3)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the fourth Na site, Na(4) is bonded to one O(1), one O(6), and two equivalent O(5) atoms to form NaO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(6), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), two equivalent Na(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Na(4), two equivalent Na(3), and one P(2) atom.
Na3PO4 is Enargite structured and crystallizes in the monoclinic Pm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form NaO4 tetrahedra that share corners with two equivalent Na(1)O4 tetrahedra, corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(3)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Na(1)-O(1) bond length is 2.30 Å. The Na(1)-O(2) bond length is 2.26 Å. The Na(1)-O(3) bond length is 2.30 Å. The Na(1)-O(5) bond length is 2.34 Å. In the second Na site, Na(2) is bonded to one O(2), one O(4), and two equivalent O(3) atoms to form NaO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. The Na(2)-O(2) bond length is 2.31 Å. The Na(2)-O(4) bond length is 2.29 Å. Both Na(2)-O(3) bond lengths are 2.39 Å. In the third Na site, Na(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form NaO4 tetrahedra that share corners with two equivalent Na(1)O4 tetrahedra, corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(3)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Na(3)-O(3) bond length is 2.35 Å. The Na(3)-O(4) bond length is 2.30 Å. The Na(3)-O(5) bond length is 2.32 Å. The Na(3)-O(6) bond length is 2.27 Å. In the fourth Na site, Na(4) is bonded to one O(1), one O(6), and two equivalent O(5) atoms to form NaO4 tetrahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. The Na(4)-O(1) bond length is 2.34 Å. The Na(4)-O(6) bond length is 2.28 Å. Both Na(4)-O(5) bond lengths are 2.39 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.56 Å. Both P(1)-O(5) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(6), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Na(2)O4 tetrahedra, corners with two equivalent Na(4)O4 tetrahedra, corners with four equivalent Na(1)O4 tetrahedra, and corners with four equivalent Na(3)O4 tetrahedra. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.56 Å. Both P(2)-O(3) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), two equivalent Na(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal pyramidal geometry to one Na(2), two equivalent Na(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Na(3), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Na(4), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Na(4), two equivalent Na(3), and one P(2) atom.