Na3In(PO4)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent In(1)O6 octahedra. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(4), two equivalent O(3), two equivalent O(5), and three equivalent O(6) atoms. In(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form InO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Na(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with three equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. In the second P site, P(2) is bonded to one O(4), one O(6), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with three equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-54°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(3), one In(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), three equivalent Na(3), and one P(2) atom.
Na3In(PO4)2 crystallizes in the monoclinic P2_1/m space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(2), one O(6), two equivalent O(3), and two equivalent O(5) atoms to form NaO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent In(1)O6 octahedra. The Na(1)-O(2) bond length is 2.34 Å. The Na(1)-O(6) bond length is 2.33 Å. Both Na(1)-O(3) bond lengths are 2.51 Å. Both Na(1)-O(5) bond lengths are 2.55 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(1), one O(2), two equivalent O(3), and two equivalent O(5) atoms. The Na(2)-O(1) bond length is 2.42 Å. The Na(2)-O(2) bond length is 2.31 Å. Both Na(2)-O(3) bond lengths are 2.86 Å. Both Na(2)-O(5) bond lengths are 2.42 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(4), two equivalent O(3), two equivalent O(5), and three equivalent O(6) atoms. The Na(3)-O(4) bond length is 2.43 Å. Both Na(3)-O(3) bond lengths are 2.46 Å. Both Na(3)-O(5) bond lengths are 2.79 Å. There is one shorter (2.29 Å) and two longer (2.92 Å) Na(3)-O(6) bond lengths. In(1) is bonded to one O(1), one O(4), two equivalent O(3), and two equivalent O(5) atoms to form InO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and edges with two equivalent Na(1)O6 octahedra. The In(1)-O(1) bond length is 2.17 Å. The In(1)-O(4) bond length is 2.16 Å. Both In(1)-O(3) bond lengths are 2.20 Å. Both In(1)-O(5) bond lengths are 2.21 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with three equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-58°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.52 Å. Both P(1)-O(3) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(4), one O(6), and two equivalent O(5) atoms to form PO4 tetrahedra that share corners with three equivalent Na(1)O6 octahedra and corners with three equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-54°. The P(2)-O(4) bond length is 1.55 Å. The P(2)-O(6) bond length is 1.52 Å. Both P(2)-O(5) bond lengths are 1.58 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), and one P(1) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(3), one In(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), three equivalent Na(3), and one P(2) atom.