Na2In2Mo5O16 crystallizes in the trigonal P3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(4) and three equivalent O(7) atoms. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(3) and three equivalent O(5) atoms to form MoO4 tetrahedra that share corners with three equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles are 24°. In the second Mo site, Mo(2) is bonded to one O(2), one O(8), two equivalent O(6), and two equivalent O(7) atoms to form MoO6 octahedra that share corners with two equivalent In(1)O6 octahedra, corners with two equivalent In(2)O6 octahedra, and edges with four equivalent Mo(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. In the third Mo site, Mo(3) is bonded to one O(4) and three equivalent O(1) atoms to form distorted MoO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles are 24°. There are two inequivalent In sites. In the first In site, In(1) is bonded to three equivalent O(1) and three equivalent O(6) atoms to form InO6 octahedra that share corners with six equivalent Mo(2)O6 octahedra and corners with three equivalent Mo(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. In the second In site, In(2) is bonded to three equivalent O(5) and three equivalent O(7) atoms to form InO6 octahedra that share corners with six equivalent Mo(2)O6 octahedra and corners with three equivalent Mo(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Mo(3), and one In(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to three equivalent Mo(2) atoms. In the third O site, O(3) is bonded in a single-bond geometry to one Mo(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one Na(2) and one Mo(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Mo(1), and one In(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to two equivalent Mo(2) and one In(1) atom. In the seventh O site, O(7) is bonded to one Na(2), two equivalent Mo(2), and one In(2) atom to form a mixture of distorted edge and corner-sharing ONaInMo2 tetrahedra. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to three equivalent Mo(2) atoms.
Na2In2Mo5O16 crystallizes in the trigonal P3m1 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to three equivalent O(1) and three equivalent O(5) atoms. All Na(1)-O(1) bond lengths are 2.55 Å. All Na(1)-O(5) bond lengths are 2.59 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(4) and three equivalent O(7) atoms. The Na(2)-O(4) bond length is 2.22 Å. All Na(2)-O(7) bond lengths are 2.45 Å. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(3) and three equivalent O(5) atoms to form MoO4 tetrahedra that share corners with three equivalent In(2)O6 octahedra. The corner-sharing octahedral tilt angles are 24°. The Mo(1)-O(3) bond length is 1.73 Å. All Mo(1)-O(5) bond lengths are 1.84 Å. In the second Mo site, Mo(2) is bonded to one O(2), one O(8), two equivalent O(6), and two equivalent O(7) atoms to form MoO6 octahedra that share corners with two equivalent In(1)O6 octahedra, corners with two equivalent In(2)O6 octahedra, and edges with four equivalent Mo(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. The Mo(2)-O(2) bond length is 2.11 Å. The Mo(2)-O(8) bond length is 2.11 Å. Both Mo(2)-O(6) bond lengths are 2.03 Å. Both Mo(2)-O(7) bond lengths are 2.08 Å. In the third Mo site, Mo(3) is bonded to one O(4) and three equivalent O(1) atoms to form distorted MoO4 tetrahedra that share corners with three equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles are 24°. The Mo(3)-O(4) bond length is 1.76 Å. All Mo(3)-O(1) bond lengths are 1.83 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to three equivalent O(1) and three equivalent O(6) atoms to form InO6 octahedra that share corners with six equivalent Mo(2)O6 octahedra and corners with three equivalent Mo(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 52°. All In(1)-O(1) bond lengths are 2.20 Å. All In(1)-O(6) bond lengths are 2.19 Å. In the second In site, In(2) is bonded to three equivalent O(5) and three equivalent O(7) atoms to form InO6 octahedra that share corners with six equivalent Mo(2)O6 octahedra and corners with three equivalent Mo(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. All In(2)-O(5) bond lengths are 2.26 Å. All In(2)-O(7) bond lengths are 2.18 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Mo(3), and one In(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to three equivalent Mo(2) atoms. In the third O site, O(3) is bonded in a single-bond geometry to one Mo(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one Na(2) and one Mo(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Mo(1), and one In(2) atom. In the sixth O site, O(6) is bonded in a trigonal planar geometry to two equivalent Mo(2) and one In(1) atom. In the seventh O site, O(7) is bonded to one Na(2), two equivalent Mo(2), and one In(2) atom to form a mixture of distorted edge and corner-sharing ONaInMo2 tetrahedra. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to three equivalent Mo(2) atoms.