W5P2O19 crystallizes in the monoclinic P2_1 space group. There are five inequivalent W sites. In the first W site, W(1) is bonded to one O(12), one O(13), one O(4), one O(8), and two equivalent O(1) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with three equivalent W(5)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 4-12°. In the second W site, W(2) is bonded to one O(16), one O(17), one O(2), one O(3), one O(6), and one O(7) atom to form WO6 octahedra that share  a cornercorner with one W(3)O6 octahedra, corners with two equivalent W(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the third W site, W(3) is bonded to one O(11), one O(18), one O(19), one O(2), and two equivalent O(5) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. In the fourth W site, W(4) is bonded to one O(10), one O(11), one O(18), one O(19), one O(6), and one O(7) atom to form WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with three equivalent W(3)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-12°. In the fifth W site, W(5) is bonded to one O(12), one O(13), one O(14), one O(15), one O(8), and one O(9) atom to form WO6 octahedra that share corners with three equivalent W(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 4-12°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(15), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, and corners with two equivalent W(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-23°. In the second P site, P(2) is bonded to one O(10), one O(16), one O(17), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one W(4)O6 octahedra,  a cornercorner with one W(5)O6 octahedra, and corners with two equivalent W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-23°. There are nineteen inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent W(1) atoms. In the second O site, O(2) is bonded in a linear geometry to one W(2) and one W(3) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one W(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent W(3) atoms. In the sixth O site, O(6) is bonded in a linear geometry to one W(2) and one W(4) atom. In the seventh O site, O(7) is bonded in a linear geometry to one W(2) and one W(4) atom. In the eighth O site, O(8) is bonded in a linear geometry to one W(1) and one W(5) atom. In the ninth O site, O(9) is bonded in a linear geometry to one W(5) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one W(4) and one P(2) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one W(3) and one W(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one W(1) and one W(5) atom. In the thirteenth O site, O(13) is bonded in a linear geometry to one W(1) and one W(5) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one W(5) and one P(1) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one W(5) and one P(1) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one W(2) and one P(2) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one W(2) and one P(2) atom. In the eighteenth O site, O(18) is bonded in a linear geometry to one W(3) and one W(4) atom. In the nineteenth O site, O(19) is bonded in a linear geometry to one W(3) and one W(4) atom.
W5P2O19 crystallizes in the monoclinic P2_1 space group. There are five inequivalent W sites. In the first W site, W(1) is bonded to one O(12), one O(13), one O(4), one O(8), and two equivalent O(1) atoms to form WO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with three equivalent W(5)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 4-12°. The W(1)-O(12) bond length is 2.02 Å. The W(1)-O(13) bond length is 1.96 Å. The W(1)-O(4) bond length is 2.04 Å. The W(1)-O(8) bond length is 2.01 Å. There is one shorter (1.85 Å) and one longer (2.00 Å) W(1)-O(1) bond length. In the second W site, W(2) is bonded to one O(16), one O(17), one O(2), one O(3), one O(6), and one O(7) atom to form WO6 octahedra that share  a cornercorner with one W(3)O6 octahedra, corners with two equivalent W(4)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 0-12°. The W(2)-O(16) bond length is 2.04 Å. The W(2)-O(17) bond length is 2.05 Å. The W(2)-O(2) bond length is 1.85 Å. The W(2)-O(3) bond length is 2.00 Å. The W(2)-O(6) bond length is 1.87 Å. The W(2)-O(7) bond length is 1.87 Å. In the third W site, W(3) is bonded to one O(11), one O(18), one O(19), one O(2), and two equivalent O(5) atoms to form corner-sharing WO6 octahedra. The corner-sharing octahedral tilt angles range from 0-10°. The W(3)-O(11) bond length is 1.95 Å. The W(3)-O(18) bond length is 1.96 Å. The W(3)-O(19) bond length is 1.96 Å. The W(3)-O(2) bond length is 2.00 Å. There is one shorter (1.91 Å) and one longer (1.92 Å) W(3)-O(5) bond length. In the fourth W site, W(4) is bonded to one O(10), one O(11), one O(18), one O(19), one O(6), and one O(7) atom to form WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with three equivalent W(3)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-12°. The W(4)-O(10) bond length is 2.04 Å. The W(4)-O(11) bond length is 1.89 Å. The W(4)-O(18) bond length is 1.89 Å. The W(4)-O(19) bond length is 1.89 Å. The W(4)-O(6) bond length is 2.00 Å. The W(4)-O(7) bond length is 1.99 Å. In the fifth W site, W(5) is bonded to one O(12), one O(13), one O(14), one O(15), one O(8), and one O(9) atom to form WO6 octahedra that share corners with three equivalent W(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 4-12°. The W(5)-O(12) bond length is 1.83 Å. The W(5)-O(13) bond length is 1.89 Å. The W(5)-O(14) bond length is 2.03 Å. The W(5)-O(15) bond length is 2.03 Å. The W(5)-O(8) bond length is 1.85 Å. The W(5)-O(9) bond length is 2.01 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(15), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, and corners with two equivalent W(5)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-23°. The P(1)-O(14) bond length is 1.54 Å. The P(1)-O(15) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(10), one O(16), one O(17), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one W(4)O6 octahedra,  a cornercorner with one W(5)O6 octahedra, and corners with two equivalent W(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-23°. The P(2)-O(10) bond length is 1.54 Å. The P(2)-O(16) bond length is 1.54 Å. The P(2)-O(17) bond length is 1.54 Å. The P(2)-O(9) bond length is 1.54 Å. There are nineteen inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent W(1) atoms. In the second O site, O(2) is bonded in a linear geometry to one W(2) and one W(3) atom. In the third O site, O(3) is bonded in a distorted linear geometry to one W(2) and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one W(1) and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to two equivalent W(3) atoms. In the sixth O site, O(6) is bonded in a linear geometry to one W(2) and one W(4) atom. In the seventh O site, O(7) is bonded in a linear geometry to one W(2) and one W(4) atom. In the eighth O site, O(8) is bonded in a linear geometry to one W(1) and one W(5) atom. In the ninth O site, O(9) is bonded in a linear geometry to one W(5) and one P(2) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one W(4) and one P(2) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one W(3) and one W(4) atom. In the twelfth O site, O(12) is bonded in a linear geometry to one W(1) and one W(5) atom. In the thirteenth O site, O(13) is bonded in a linear geometry to one W(1) and one W(5) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one W(5) and one P(1) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one W(5) and one P(1) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to one W(2) and one P(2) atom. In the seventeenth O site, O(17) is bonded in a bent 150 degrees geometry to one W(2) and one P(2) atom. In the eighteenth O site, O(18) is bonded in a linear geometry to one W(3) and one W(4) atom. In the nineteenth O site, O(19) is bonded in a linear geometry to one W(3) and one W(4) atom.