Na4LaZn(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 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) 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. La(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form LaO6 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 La(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. 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 face-sharing ONa3ZnP trigonal bipyramids. In the second O site, O(4) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), one La(1), and one P(1) atom. 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 3-coordinate geometry to one Na(1), one La(1), and one P(1) atom.
Na4LaZn(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 5-coordinate geometry to one O(1), one O(2), one O(4), and two equivalent O(3) atoms. The Na(1)-O(1) bond length is 2.56 Å. The Na(1)-O(2) bond length is 2.75 Å. The Na(1)-O(4) bond length is 2.45 Å. There is one shorter (2.44 Å) and one longer (2.56 Å) Na(1)-O(3) 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 2.35 Å. All Na(2)-O(4) bond lengths are 2.88 Å. La(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form LaO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All La(1)-O(2) bond lengths are 2.32 Å. All La(1)-O(4) bond lengths are 2.40 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 2.13 Å. All Zn(1)-O(3) bond lengths are 2.36 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 La(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 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 face-sharing ONa3ZnP trigonal bipyramids. In the second O site, O(4) is bonded in a 1-coordinate geometry to one Na(1), one Na(2), one La(1), and one P(1) atom. 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 3-coordinate geometry to one Na(1), one La(1), and one P(1) atom.