Na3In2(PO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(4) atoms. In the third Na site, Na(3) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent In(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. In(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form InO6 octahedra that share  a cornercorner with one Na(3)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one In(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra and corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-59°. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra and corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-66°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(3), one In(1), and one P(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one In(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(2), one In(1), 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), two equivalent Na(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent In(1) and one P(1) atom.
Na3In2(PO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both Na(1)-O(2) bond lengths are 2.49 Å. Both Na(1)-O(3) bond lengths are 2.48 Å. Both Na(1)-O(5) bond lengths are 2.47 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(4) atoms. Both Na(2)-O(2) bond lengths are 2.74 Å. There are two shorter (2.51 Å) and two longer (2.59 Å) Na(2)-O(4) bond lengths. In the third Na site, Na(3) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent In(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Na(3)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. Both Na(3)-O(1) bond lengths are 2.43 Å. There are two shorter (2.38 Å) and two longer (2.63 Å) Na(3)-O(5) bond lengths. In(1) is bonded to one O(1), one O(2), one O(3), one O(4), and two equivalent O(6) atoms to form InO6 octahedra that share  a cornercorner with one Na(3)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one In(1)O6 octahedra. The corner-sharing octahedral tilt angles are 65°. The In(1)-O(1) bond length is 2.12 Å. The In(1)-O(2) bond length is 2.16 Å. The In(1)-O(3) bond length is 2.14 Å. The In(1)-O(4) bond length is 2.17 Å. There is one shorter (2.26 Å) and one longer (2.28 Å) In(1)-O(6) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra and corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-59°. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(5) bond length is 1.52 Å. The P(1)-O(6) bond length is 1.58 Å. In the second P site, P(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Na(3)O6 octahedra and corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-66°. Both P(2)-O(1) bond lengths are 1.56 Å. Both P(2)-O(2) bond lengths are 1.55 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Na(3), one In(1), and one P(2) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one In(1), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(2), one In(1), 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), two equivalent Na(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to two equivalent In(1) and one P(1) atom.