W5P2O19 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(5), and one O(6) atom to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-14°. In the second W site, W(2) is bonded to one O(1), one O(4), one O(6), one O(7), one O(8), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one W(3)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the third W site, W(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. P(1) is bonded to one O(4), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra and corners with three equivalent W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-25°. There are ten inequivalent O sites. In the first O site, O(9) is bonded in a bent 150 degrees geometry to one W(2) and one P(1) atom. In the second O site, O(1) is bonded in a linear geometry to one W(1) and one W(2) atom. In the third O site, O(2) is bonded in a linear geometry to one W(1) and one W(3) atom. In the fourth O site, O(3) is bonded in a linear geometry to one W(1) and one W(3) atom. In the fifth O site, O(4) is bonded in a linear geometry to one W(2) and one P(1) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a linear geometry to one W(1) and one W(2) atom. In the eighth O site, O(10) is bonded in a linear geometry to two equivalent W(1) atoms. In the ninth O site, O(7) is bonded in a linear geometry to one W(2) and one P(1) atom. In the tenth O site, O(8) is bonded in a linear geometry to one W(2) and one W(3) atom.
W5P2O19 crystallizes in the monoclinic P2_1/c space group. There are three inequivalent W sites. In the first W site, W(1) is bonded to one O(1), one O(10), one O(2), one O(3), one O(5), and one O(6) atom to form WO6 octahedra that share  a cornercorner with one W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, corners with two equivalent W(3)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-14°. The W(1)-O(1) bond length is 1.99 Å. The W(1)-O(10) bond length is 1.92 Å. The W(1)-O(2) bond length is 1.89 Å. The W(1)-O(3) bond length is 1.91 Å. The W(1)-O(5) bond length is 2.05 Å. The W(1)-O(6) bond length is 1.98 Å. In the second W site, W(2) is bonded to one O(1), one O(4), one O(6), one O(7), one O(8), and one O(9) atom to form WO6 octahedra that share  a cornercorner with one W(3)O6 octahedra, corners with two equivalent W(1)O6 octahedra, and corners with three equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-14°. The W(2)-O(1) bond length is 1.86 Å. The W(2)-O(4) bond length is 2.04 Å. The W(2)-O(6) bond length is 1.87 Å. The W(2)-O(7) bond length is 2.00 Å. The W(2)-O(8) bond length is 1.86 Å. The W(2)-O(9) bond length is 2.04 Å. In the third W site, W(3) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(8) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 2-11°. Both W(3)-O(2) bond lengths are 1.94 Å. Both W(3)-O(3) bond lengths are 1.93 Å. Both W(3)-O(8) bond lengths are 1.96 Å. P(1) is bonded to one O(4), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra and corners with three equivalent W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-25°. The P(1)-O(4) bond length is 1.54 Å. The P(1)-O(5) bond length is 1.53 Å. The P(1)-O(7) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.54 Å. There are ten inequivalent O sites. In the first O site, O(9) is bonded in a bent 150 degrees geometry to one W(2) and one P(1) atom. In the second O site, O(1) is bonded in a linear geometry to one W(1) and one W(2) atom. In the third O site, O(2) is bonded in a linear geometry to one W(1) and one W(3) atom. In the fourth O site, O(3) is bonded in a linear geometry to one W(1) and one W(3) atom. In the fifth O site, O(4) is bonded in a linear geometry to one W(2) and one P(1) atom. In the sixth O site, O(5) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the seventh O site, O(6) is bonded in a linear geometry to one W(1) and one W(2) atom. In the eighth O site, O(10) is bonded in a linear geometry to two equivalent W(1) atoms. In the ninth O site, O(7) is bonded in a linear geometry to one W(2) and one P(1) atom. In the tenth O site, O(8) is bonded in a linear geometry to one W(2) and one W(3) atom.