Na3In2(AsO4)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(6) and four equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. In(1) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms to form InO6 octahedra that share corners with two equivalent As(2)O4 tetrahedra, corners with four equivalent As(1)O4 tetrahedra, and  an edgeedge with one In(1)O6 octahedra. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form AsO4 tetrahedra that share corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. In the second As site, As(2) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form AsO4 tetrahedra that share corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(3), one In(1), and one As(1) atom to form a mixture of distorted corner and edge-sharing ONa2InAs trigonal pyramids. In the second O site, O(2) is bonded to one Na(2), one Na(3), one In(1), and one As(1) atom to form a mixture of distorted corner and edge-sharing ONa2InAs trigonal pyramids. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one In(1), and one As(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent In(1) and one As(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Na(1), one In(1), and one As(2) atom.
Na3In2(AsO4)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(6) and four equivalent O(4) atoms. Both Na(1)-O(6) bond lengths are 2.40 Å. There are two shorter (2.36 Å) and two longer (2.59 Å) Na(1)-O(4) bond lengths. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. Both Na(2)-O(2) bond lengths are 2.41 Å. Both Na(2)-O(3) bond lengths are 2.41 Å. Both Na(2)-O(4) bond lengths are 2.36 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(2) and four equivalent O(1) atoms. Both Na(3)-O(2) bond lengths are 2.76 Å. There are two shorter (2.49 Å) and two longer (2.50 Å) Na(3)-O(1) bond lengths. In(1) is bonded to one O(1), one O(2), one O(3), one O(6), and two equivalent O(5) atoms to form InO6 octahedra that share corners with two equivalent As(2)O4 tetrahedra, corners with four equivalent As(1)O4 tetrahedra, and  an edgeedge with one In(1)O6 octahedra. The In(1)-O(1) bond length is 2.16 Å. The In(1)-O(2) bond length is 2.14 Å. The In(1)-O(3) bond length is 2.14 Å. The In(1)-O(6) bond length is 2.10 Å. There is one shorter (2.22 Å) and one longer (2.26 Å) In(1)-O(5) bond length. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form AsO4 tetrahedra that share corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-59°. The As(1)-O(1) bond length is 1.72 Å. The As(1)-O(2) bond length is 1.70 Å. The As(1)-O(4) bond length is 1.66 Å. The As(1)-O(5) bond length is 1.72 Å. In the second As site, As(2) is bonded to two equivalent O(3) and two equivalent O(6) atoms to form AsO4 tetrahedra that share corners with four equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-55°. Both As(2)-O(3) bond lengths are 1.70 Å. Both As(2)-O(6) bond lengths are 1.70 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(3), one In(1), and one As(1) atom to form a mixture of distorted corner and edge-sharing ONa2InAs trigonal pyramids. In the second O site, O(2) is bonded to one Na(2), one Na(3), one In(1), and one As(1) atom to form a mixture of distorted corner and edge-sharing ONa2InAs trigonal pyramids. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one In(1), and one As(2) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one As(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to two equivalent In(1) and one As(1) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to one Na(1), one In(1), and one As(2) atom.