Rb5In(MoO4)4 crystallizes in the monoclinic P2/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one O(2), one O(4), one O(5), one O(7), two equivalent O(1), and two equivalent O(6) atoms. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one O(1), one O(4), one O(5), two equivalent O(7), two equivalent O(8), and three equivalent O(3) atoms. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(7), and two equivalent O(8) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form MoO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra. The corner-sharing octahedral tilt angles are 44°. In the second Mo site, Mo(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form MoO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-44°. In(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form InO6 octahedra that share corners with two equivalent Mo(1)O4 tetrahedra and corners with four equivalent Mo(2)O4 tetrahedra. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one Mo(1) atom. In the second O site, O(5) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one Mo(2), and one In(1) atom. In the third O site, O(6) is bonded in a 1-coordinate geometry to two equivalent Rb(1) and one Mo(2) atom. In the fourth O site, O(7) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and one Mo(1) atom. In the fifth O site, O(8) is bonded in a 4-coordinate geometry to one Rb(3), two equivalent Rb(2), and one Mo(1) atom. In the sixth O site, O(1) is bonded in a 2-coordinate geometry to one Rb(2), two equivalent Rb(1), one Mo(2), and one In(1) atom. In the seventh O site, O(2) is bonded in a 2-coordinate geometry to one Rb(1), one Mo(1), and one In(1) atom. In the eighth O site, O(3) is bonded in a distorted single-bond geometry to one Rb(3), three equivalent Rb(2), and one Mo(2) atom.
Rb5In(MoO4)4 crystallizes in the monoclinic P2/c space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one O(2), one O(4), one O(5), one O(7), two equivalent O(1), and two equivalent O(6) atoms. The Rb(1)-O(2) bond length is 3.17 Å. The Rb(1)-O(4) bond length is 2.85 Å. The Rb(1)-O(5) bond length is 3.01 Å. The Rb(1)-O(7) bond length is 3.00 Å. There is one shorter (3.01 Å) and one longer (3.09 Å) Rb(1)-O(1) bond length. There is one shorter (2.75 Å) and one longer (3.26 Å) Rb(1)-O(6) bond length. In the second Rb site, Rb(2) is bonded in a 10-coordinate geometry to one O(1), one O(4), one O(5), two equivalent O(7), two equivalent O(8), and three equivalent O(3) atoms. The Rb(2)-O(1) bond length is 3.50 Å. The Rb(2)-O(4) bond length is 2.97 Å. The Rb(2)-O(5) bond length is 3.38 Å. There is one shorter (2.91 Å) and one longer (3.07 Å) Rb(2)-O(7) bond length. There is one shorter (2.78 Å) and one longer (3.01 Å) Rb(2)-O(8) bond length. There are a spread of Rb(2)-O(3) bond distances ranging from 3.08-3.14 Å. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to two equivalent O(3), two equivalent O(7), and two equivalent O(8) atoms. Both Rb(3)-O(3) bond lengths are 2.96 Å. Both Rb(3)-O(7) bond lengths are 2.90 Å. Both Rb(3)-O(8) bond lengths are 2.90 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(2), one O(4), one O(7), and one O(8) atom to form MoO4 tetrahedra that share  a cornercorner with one In(1)O6 octahedra. The corner-sharing octahedral tilt angles are 44°. The Mo(1)-O(2) bond length is 1.83 Å. The Mo(1)-O(4) bond length is 1.75 Å. The Mo(1)-O(7) bond length is 1.76 Å. The Mo(1)-O(8) bond length is 1.74 Å. In the second Mo site, Mo(2) is bonded to one O(1), one O(3), one O(5), and one O(6) atom to form MoO4 tetrahedra that share corners with two equivalent In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-44°. The Mo(2)-O(1) bond length is 1.81 Å. The Mo(2)-O(3) bond length is 1.74 Å. The Mo(2)-O(5) bond length is 1.80 Å. The Mo(2)-O(6) bond length is 1.73 Å. In(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form InO6 octahedra that share corners with two equivalent Mo(1)O4 tetrahedra and corners with four equivalent Mo(2)O4 tetrahedra. Both In(1)-O(1) bond lengths are 2.18 Å. Both In(1)-O(2) bond lengths are 2.14 Å. Both In(1)-O(5) bond lengths are 2.20 Å. There are eight inequivalent O sites. In the first O site, O(4) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), and one Mo(1) atom. In the second O site, O(5) is bonded in a 2-coordinate geometry to one Rb(1), one Rb(2), one Mo(2), and one In(1) atom. In the third O site, O(6) is bonded in a 1-coordinate geometry to two equivalent Rb(1) and one Mo(2) atom. In the fourth O site, O(7) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and one Mo(1) atom. In the fifth O site, O(8) is bonded in a 4-coordinate geometry to one Rb(3), two equivalent Rb(2), and one Mo(1) atom. In the sixth O site, O(1) is bonded in a 2-coordinate geometry to one Rb(2), two equivalent Rb(1), one Mo(2), and one In(1) atom. In the seventh O site, O(2) is bonded in a 2-coordinate geometry to one Rb(1), one Mo(1), and one In(1) atom. In the eighth O site, O(3) is bonded in a distorted single-bond geometry to one Rb(3), three equivalent Rb(2), and one Mo(2) atom.