CsMn2(PO3)6 crystallizes in the triclinic P-1 space group. Cs(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(8), and two equivalent O(9) atoms to form distorted CsO8 hexagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(3)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Cs(1)O8 hexagonal bipyramids. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(7), and two equivalent O(9) atoms to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cs(1)O8 hexagonal bipyramids. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cs(1)O8 hexagonal bipyramid, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-49°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cs(1)O8 hexagonal bipyramid, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-49°. In the third P site, P(3) is bonded to one O(4), one O(5), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cs(1)O8 hexagonal bipyramids,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)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 range from 53-54°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(2), and one P(3) atom.
CsMn2(PO3)6 crystallizes in the triclinic P-1 space group. Cs(1) is bonded to two equivalent O(1), two equivalent O(2), two equivalent O(8), and two equivalent O(9) atoms to form distorted CsO8 hexagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(3)O4 tetrahedra, edges with two equivalent Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O6 octahedra. Both Cs(1)-O(1) bond lengths are 3.56 Å. Both Cs(1)-O(2) bond lengths are 3.56 Å. Both Cs(1)-O(8) bond lengths are 3.38 Å. Both Cs(1)-O(9) bond lengths are 3.35 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(6), and two equivalent O(8) atoms to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Cs(1)O8 hexagonal bipyramids. Both Mn(1)-O(1) bond lengths are 2.18 Å. Both Mn(1)-O(6) bond lengths are 2.03 Å. Both Mn(1)-O(8) bond lengths are 2.14 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(7), and two equivalent O(9) atoms to form MnO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Cs(1)O8 hexagonal bipyramids. Both Mn(2)-O(2) bond lengths are 2.18 Å. Both Mn(2)-O(7) bond lengths are 2.05 Å. Both Mn(2)-O(9) bond lengths are 2.16 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(3), one O(4), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Cs(1)O8 hexagonal bipyramid, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-49°. The P(1)-O(1) bond length is 1.50 Å. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(4) bond length is 1.61 Å. The P(1)-O(6) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Cs(1)O8 hexagonal bipyramid, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-49°. The P(2)-O(2) bond length is 1.50 Å. The P(2)-O(3) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.61 Å. The P(2)-O(7) bond length is 1.50 Å. In the third P site, P(3) is bonded to one O(4), one O(5), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Cs(1)O8 hexagonal bipyramids,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)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 range from 53-54°. The P(3)-O(4) bond length is 1.60 Å. The P(3)-O(5) bond length is 1.60 Å. The P(3)-O(8) bond length is 1.51 Å. The P(3)-O(9) bond length is 1.51 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(2), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 2-coordinate geometry to one Cs(1), one Mn(2), and one P(3) atom.