Na3In2(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(5), one O(6), one O(8), and two equivalent O(3) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form InO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. In the second In site, In(2) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form InO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-43°. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-42°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-41°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(3) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one In(2), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(3), one In(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one In(1) and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(3), one In(1), and one P(2) atom to form distorted corner-sharing ONa2InP trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one In(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(2), one In(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), one In(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one In(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one In(1), and one P(1) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(2), one Na(3), one In(2), and one P(1) atom to form distorted corner-sharing ONa3InP trigonal bipyramids.
Na3In2(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.62 Å. The Na(1)-O(11) bond length is 2.40 Å. The Na(1)-O(12) bond length is 2.60 Å. The Na(1)-O(2) bond length is 2.42 Å. The Na(1)-O(5) bond length is 2.50 Å. The Na(1)-O(6) bond length is 2.51 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.52 Å. The Na(2)-O(10) bond length is 2.65 Å. The Na(2)-O(11) bond length is 2.48 Å. The Na(2)-O(12) bond length is 2.61 Å. The Na(2)-O(2) bond length is 2.52 Å. The Na(2)-O(7) bond length is 2.95 Å. The Na(2)-O(8) bond length is 2.96 Å. The Na(2)-O(9) bond length is 2.53 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(12), one O(5), one O(6), one O(8), and two equivalent O(3) atoms. The Na(3)-O(1) bond length is 2.64 Å. The Na(3)-O(12) bond length is 2.50 Å. The Na(3)-O(5) bond length is 2.54 Å. The Na(3)-O(6) bond length is 2.50 Å. The Na(3)-O(8) bond length is 2.43 Å. There is one shorter (2.80 Å) and one longer (2.89 Å) Na(3)-O(3) bond length. There are two inequivalent In sites. In the first In site, In(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form InO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The In(1)-O(1) bond length is 2.24 Å. The In(1)-O(11) bond length is 2.18 Å. The In(1)-O(4) bond length is 2.09 Å. The In(1)-O(5) bond length is 2.18 Å. The In(1)-O(8) bond length is 2.17 Å. The In(1)-O(9) bond length is 2.16 Å. In the second In site, In(2) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form InO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The In(2)-O(10) bond length is 2.15 Å. The In(2)-O(12) bond length is 2.18 Å. The In(2)-O(2) bond length is 2.20 Å. The In(2)-O(3) bond length is 2.15 Å. The In(2)-O(6) bond length is 2.20 Å. The In(2)-O(7) bond length is 2.10 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-43°. The P(1)-O(11) bond length is 1.55 Å. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-42°. The P(2)-O(2) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.55 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra and corners with two equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-41°. The P(3)-O(1) bond length is 1.57 Å. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(6) bond length is 1.55 Å. The P(3)-O(8) bond length is 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(3) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one In(2), and one P(2) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to two equivalent Na(3), one In(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one In(1) and one P(1) atom. In the fifth O site, O(5) is bonded to one Na(1), one Na(3), one In(1), and one P(2) atom to form distorted corner-sharing ONa2InP trigonal pyramids. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one In(2), and one P(3) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(2), one In(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), one In(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one In(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one In(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one In(1), and one P(1) atom. In the twelfth O site, O(12) is bonded to one Na(1), one Na(2), one Na(3), one In(2), and one P(1) atom to form distorted corner-sharing ONa3InP trigonal bipyramids.