Rb4Mn(MoO4)3 crystallizes in the trigonal P31c space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to one O(5), three equivalent O(4), and six equivalent O(3) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to three equivalent O(3) and six equivalent O(4) atoms. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(6) atoms. In the fourth Rb site, Rb(4) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(6) atoms. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1) and three equivalent O(3) atoms to form MoO4 tetrahedra that share  a cornercorner with one Mn(1)O5 trigonal bipyramid. In the second Mo site, Mo(2) is bonded to one O(2) and three equivalent O(4) atoms to form MoO4 tetrahedra that share  a cornercorner with one Mn(1)O5 trigonal bipyramid. In the third Mo site, Mo(3) is bonded to one O(5) and three equivalent O(6) atoms to form MoO4 tetrahedra that share corners with three equivalent Mn(1)O5 trigonal bipyramids. Mn(1) is bonded to one O(1), one O(2), and three equivalent O(6) atoms to form MnO5 trigonal bipyramids that share  a cornercorner with one Mo(1)O4 tetrahedra,  a cornercorner with one Mo(2)O4 tetrahedra, and corners with three equivalent Mo(3)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted single-bond geometry to one Rb(1) and one Mo(3) atom. In the second O site, O(6) is bonded in a 4-coordinate geometry to one Rb(3), one Rb(4), one Mo(3), and one Mn(1) atom. In the third O site, O(1) is bonded in a linear geometry to one Mo(1) and one Mn(1) atom. In the fourth O site, O(2) is bonded in a linear geometry to one Mo(2) and one Mn(1) atom. In the fifth O site, O(3) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Mo(1) atom. In the sixth O site, O(4) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(4), two equivalent Rb(2), and one Mo(2) atom.
Rb4Mn(MoO4)3 crystallizes in the trigonal P31c space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 10-coordinate geometry to one O(5), three equivalent O(4), and six equivalent O(3) atoms. The Rb(1)-O(5) bond length is 3.04 Å. All Rb(1)-O(4) bond lengths are 3.01 Å. There are three shorter (3.07 Å) and three longer (3.39 Å) Rb(1)-O(3) bond lengths. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to three equivalent O(3) and six equivalent O(4) atoms. All Rb(2)-O(3) bond lengths are 2.92 Å. There are three shorter (3.09 Å) and three longer (3.44 Å) Rb(2)-O(4) bond lengths. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(6) atoms. All Rb(3)-O(3) bond lengths are 2.90 Å. All Rb(3)-O(6) bond lengths are 3.31 Å. In the fourth Rb site, Rb(4) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(6) atoms. All Rb(4)-O(4) bond lengths are 2.93 Å. All Rb(4)-O(6) bond lengths are 3.22 Å. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1) and three equivalent O(3) atoms to form MoO4 tetrahedra that share  a cornercorner with one Mn(1)O5 trigonal bipyramid. The Mo(1)-O(1) bond length is 1.83 Å. All Mo(1)-O(3) bond lengths are 1.79 Å. In the second Mo site, Mo(2) is bonded to one O(2) and three equivalent O(4) atoms to form MoO4 tetrahedra that share  a cornercorner with one Mn(1)O5 trigonal bipyramid. The Mo(2)-O(2) bond length is 1.82 Å. All Mo(2)-O(4) bond lengths are 1.79 Å. In the third Mo site, Mo(3) is bonded to one O(5) and three equivalent O(6) atoms to form MoO4 tetrahedra that share corners with three equivalent Mn(1)O5 trigonal bipyramids. The Mo(3)-O(5) bond length is 1.76 Å. All Mo(3)-O(6) bond lengths are 1.82 Å. Mn(1) is bonded to one O(1), one O(2), and three equivalent O(6) atoms to form MnO5 trigonal bipyramids that share  a cornercorner with one Mo(1)O4 tetrahedra,  a cornercorner with one Mo(2)O4 tetrahedra, and corners with three equivalent Mo(3)O4 tetrahedra. The Mn(1)-O(1) bond length is 2.05 Å. The Mn(1)-O(2) bond length is 2.05 Å. All Mn(1)-O(6) bond lengths are 2.20 Å. There are six inequivalent O sites. In the first O site, O(5) is bonded in a distorted single-bond geometry to one Rb(1) and one Mo(3) atom. In the second O site, O(6) is bonded in a 4-coordinate geometry to one Rb(3), one Rb(4), one Mo(3), and one Mn(1) atom. In the third O site, O(1) is bonded in a linear geometry to one Mo(1) and one Mn(1) atom. In the fourth O site, O(2) is bonded in a linear geometry to one Mo(2) and one Mn(1) atom. In the fifth O site, O(3) is bonded in a distorted single-bond geometry to one Rb(2), one Rb(3), two equivalent Rb(1), and one Mo(1) atom. In the sixth O site, O(4) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(4), two equivalent Rb(2), and one Mo(2) atom.