Na4ScZn(PO4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. Sc(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form ScO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. Zn(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form distorted ZnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. 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 corners with two equivalent Sc(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-39°. There are four inequivalent O sites. In the first O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Zn(1), and one P(1) atom to form distorted ONa3ZnP trigonal bipyramids that share corners with six equivalent O(4)Na3ScP trigonal bipyramids,  an edgeedge with one O(4)Na3ScP trigonal bipyramid, and faces with two equivalent O(3)Na3ZnP trigonal bipyramids. In the second O site, O(4) is bonded to one Na(2), two equivalent Na(1), one Sc(1), and one P(1) atom to form distorted ONa3ScP trigonal bipyramids that share corners with six equivalent O(3)Na3ZnP trigonal bipyramids,  an edgeedge with one O(3)Na3ZnP trigonal bipyramid, and faces with two equivalent O(4)Na3ScP trigonal bipyramids. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(1) atom. In the fourth O site, O(2) is bonded in a 2-coordinate geometry to one Na(1), one Sc(1), and one P(1) atom.
Na4ScZn(PO4)3 crystallizes in the trigonal R3c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.47 Å. The Na(1)-O(2) bond length is 2.74 Å. There is one shorter (2.42 Å) and one longer (2.50 Å) Na(1)-O(3) bond length. There is one shorter (2.57 Å) and one longer (2.61 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. All Na(2)-O(3) bond lengths are 2.44 Å. All Na(2)-O(4) bond lengths are 2.61 Å. Sc(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form ScO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Sc(1)-O(2) bond lengths are 2.07 Å. All Sc(1)-O(4) bond lengths are 2.15 Å. Zn(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form distorted ZnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Zn(1)-O(1) bond lengths are 2.04 Å. All Zn(1)-O(3) bond lengths are 2.26 Å. 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 corners with two equivalent Sc(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-39°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.56 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded to one Na(2), two equivalent Na(1), one Zn(1), and one P(1) atom to form distorted ONa3ZnP trigonal bipyramids that share corners with six equivalent O(4)Na3ScP trigonal bipyramids,  an edgeedge with one O(4)Na3ScP trigonal bipyramid, and faces with two equivalent O(3)Na3ZnP trigonal bipyramids. In the second O site, O(4) is bonded to one Na(2), two equivalent Na(1), one Sc(1), and one P(1) atom to form distorted ONa3ScP trigonal bipyramids that share corners with six equivalent O(3)Na3ZnP trigonal bipyramids,  an edgeedge with one O(3)Na3ZnP trigonal bipyramid, and faces with two equivalent O(4)Na3ScP trigonal bipyramids. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one P(1) atom. In the fourth O site, O(2) is bonded in a 2-coordinate geometry to one Na(1), one Sc(1), and one P(1) atom.