K2Mo3Al(P2O7)4 crystallizes in the triclinic P-1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(2), and two equivalent O(5) atoms. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(12), and two equivalent O(6) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(4), and one O(9) atom to form MoO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Mo site, Mo(2) is bonded to two equivalent O(11), two equivalent O(13), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Al(1) is bonded to two equivalent O(12), two equivalent O(14), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Mo(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-53°. In the second P site, P(2) is bonded to one O(10), one O(12), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Al(1)O6 octahedra, corners with two equivalent Mo(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-50°. In the third P site, P(3) is bonded to one O(13), one O(3), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one Al(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-45°. In the fourth P site, P(4) is bonded to one O(14), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one Al(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-45°. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one K(2), one Mo(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one Mo(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Mo(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Mo(1) and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one K(1), one Mo(2), and one P(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one K(2), one Al(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one K(1), one Mo(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one K(2), one Al(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Mo(2) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Al(1) and one P(4) atom.
K2Mo3Al(P2O7)4 crystallizes in the triclinic P-1 space group. There are two inequivalent K sites. In the first K site, K(1) is bonded in a 6-coordinate geometry to two equivalent O(11), two equivalent O(2), and two equivalent O(5) atoms. Both K(1)-O(11) bond lengths are 2.98 Å. Both K(1)-O(2) bond lengths are 2.76 Å. Both K(1)-O(5) bond lengths are 2.55 Å. In the second K site, K(2) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent O(12), and two equivalent O(6) atoms. Both K(2)-O(1) bond lengths are 2.77 Å. Both K(2)-O(12) bond lengths are 2.96 Å. Both K(2)-O(6) bond lengths are 2.61 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(4), and one O(9) atom to form MoO6 octahedra that share  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Mo(1)-O(1) bond length is 2.06 Å. The Mo(1)-O(10) bond length is 2.02 Å. The Mo(1)-O(2) bond length is 2.08 Å. The Mo(1)-O(3) bond length is 2.06 Å. The Mo(1)-O(4) bond length is 2.07 Å. The Mo(1)-O(9) bond length is 2.04 Å. In the second Mo site, Mo(2) is bonded to two equivalent O(11), two equivalent O(13), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Both Mo(2)-O(11) bond lengths are 2.08 Å. Both Mo(2)-O(13) bond lengths are 1.98 Å. Both Mo(2)-O(5) bond lengths are 1.97 Å. Al(1) is bonded to two equivalent O(12), two equivalent O(14), and two equivalent O(6) atoms to form AlO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Both Al(1)-O(12) bond lengths are 1.96 Å. Both Al(1)-O(14) bond lengths are 1.87 Å. Both Al(1)-O(6) bond lengths are 1.87 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Mo(1)O6 octahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 37-53°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(11) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.60 Å. The P(1)-O(9) bond length is 1.50 Å. In the second P site, P(2) is bonded to one O(10), one O(12), one O(2), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Al(1)O6 octahedra, corners with two equivalent Mo(1)O6 octahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 35-50°. The P(2)-O(10) bond length is 1.51 Å. The P(2)-O(12) bond length is 1.52 Å. The P(2)-O(2) bond length is 1.53 Å. The P(2)-O(8) bond length is 1.61 Å. In the third P site, P(3) is bonded to one O(13), one O(3), one O(6), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one Al(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-45°. The P(3)-O(13) bond length is 1.53 Å. The P(3)-O(3) bond length is 1.50 Å. The P(3)-O(6) bond length is 1.51 Å. The P(3)-O(8) bond length is 1.59 Å. In the fourth P site, P(4) is bonded to one O(14), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one Al(1)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-45°. The P(4)-O(14) bond length is 1.49 Å. The P(4)-O(4) bond length is 1.50 Å. The P(4)-O(5) bond length is 1.55 Å. The P(4)-O(7) bond length is 1.60 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one K(2), one Mo(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one K(1), one Mo(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Mo(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Mo(1) and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one K(1), one Mo(2), and one P(4) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one K(2), one Al(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one P(2) and one P(3) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(2) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one K(1), one Mo(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one K(2), one Al(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted bent 150 degrees geometry to one Mo(2) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one Al(1) and one P(4) atom.