RbMo3(PO7)2 crystallizes in the monoclinic P2_1/m space group. Rb(1) is bonded in a 8-coordinate geometry to one O(2), one O(5), two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(11), one O(2), one O(4), and two equivalent O(3) atoms to form distorted MoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  a cornercorner with one Mo(2)O5 trigonal bipyramid. In the second Mo site, Mo(2) is bonded to one O(1), one O(10), one O(9), and two equivalent O(6) atoms to form MoO5 trigonal bipyramids that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 21°. In the third Mo site, Mo(3) is bonded in a 6-coordinate geometry to one O(11), one O(4), one O(5), one O(8), and two equivalent O(7) atoms. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(8), one O(9), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Mo(1)O6 octahedra and  a cornercorner with one Mo(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 34°. In the second P site, P(2) is bonded to one O(10), one O(11), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra and  a cornercorner with one Mo(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 47°. There are eleven inequivalent O sites. In the first O site, O(8) is bonded in a linear geometry to one Mo(3) and one P(1) atom. In the second O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Mo(2) and one P(1) atom. In the third O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(2) and one P(2) atom. In the fourth O site, O(11) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(3), and one P(2) atom. In the fifth O site, O(1) is bonded in a bent 150 degrees geometry to one Mo(1) and one Mo(2) atom. In the sixth O site, O(2) is bonded in a distorted single-bond geometry to one Rb(1) and one Mo(1) atom. In the seventh O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Rb(1), one Mo(1), and one P(1) atom. In the eighth O site, O(4) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(3) atom. In the ninth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Rb(1) and one Mo(3) atom. In the tenth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Rb(1) and one Mo(2) atom. In the eleventh O site, O(7) is bonded in a 2-coordinate geometry to one Rb(1), one Mo(3), and one P(2) atom.
RbMo3(PO7)2 crystallizes in the monoclinic P2_1/m space group. Rb(1) is bonded in a 8-coordinate geometry to one O(2), one O(5), two equivalent O(3), two equivalent O(6), and two equivalent O(7) atoms. The Rb(1)-O(2) bond length is 2.93 Å. The Rb(1)-O(5) bond length is 2.87 Å. Both Rb(1)-O(3) bond lengths are 3.07 Å. Both Rb(1)-O(6) bond lengths are 2.85 Å. Both Rb(1)-O(7) bond lengths are 3.12 Å. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(11), one O(2), one O(4), and two equivalent O(3) atoms to form distorted MoO6 octahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and  a cornercorner with one Mo(2)O5 trigonal bipyramid. The Mo(1)-O(1) bond length is 1.89 Å. The Mo(1)-O(11) bond length is 2.34 Å. The Mo(1)-O(2) bond length is 1.71 Å. The Mo(1)-O(4) bond length is 1.89 Å. Both Mo(1)-O(3) bond lengths are 2.04 Å. In the second Mo site, Mo(2) is bonded to one O(1), one O(10), one O(9), and two equivalent O(6) atoms to form MoO5 trigonal bipyramids that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 21°. The Mo(2)-O(1) bond length is 1.99 Å. The Mo(2)-O(10) bond length is 2.03 Å. The Mo(2)-O(9) bond length is 2.05 Å. Both Mo(2)-O(6) bond lengths are 1.73 Å. In the third Mo site, Mo(3) is bonded in a 6-coordinate geometry to one O(11), one O(4), one O(5), one O(8), and two equivalent O(7) atoms. The Mo(3)-O(11) bond length is 2.37 Å. The Mo(3)-O(4) bond length is 2.01 Å. The Mo(3)-O(5) bond length is 1.71 Å. The Mo(3)-O(8) bond length is 2.07 Å. Both Mo(3)-O(7) bond lengths are 2.04 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(8), one O(9), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with two equivalent Mo(1)O6 octahedra and  a cornercorner with one Mo(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 34°. The P(1)-O(8) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.55 Å. Both P(1)-O(3) bond lengths are 1.55 Å. In the second P site, P(2) is bonded to one O(10), one O(11), and two equivalent O(7) atoms to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra and  a cornercorner with one Mo(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 47°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(11) bond length is 1.55 Å. Both P(2)-O(7) bond lengths are 1.55 Å. There are eleven inequivalent O sites. In the first O site, O(8) is bonded in a linear geometry to one Mo(3) and one P(1) atom. In the second O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Mo(2) and one P(1) atom. In the third O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(2) and one P(2) atom. In the fourth O site, O(11) is bonded in a distorted single-bond geometry to one Mo(1), one Mo(3), and one P(2) atom. In the fifth O site, O(1) is bonded in a bent 150 degrees geometry to one Mo(1) and one Mo(2) atom. In the sixth O site, O(2) is bonded in a distorted single-bond geometry to one Rb(1) and one Mo(1) atom. In the seventh O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Rb(1), one Mo(1), and one P(1) atom. In the eighth O site, O(4) is bonded in a bent 120 degrees geometry to one Mo(1) and one Mo(3) atom. In the ninth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Rb(1) and one Mo(3) atom. In the tenth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Rb(1) and one Mo(2) atom. In the eleventh O site, O(7) is bonded in a 2-coordinate geometry to one Rb(1), one Mo(3), and one P(2) atom.