LiP(WO4)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(16), one O(3), one O(4), one O(7), and one O(9) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(1), one O(13), and one O(8) atom. There are four inequivalent W sites. In the first W site, W(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form WO6 octahedra that share corners with three equivalent W(3)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 1-31°. In the second W site, W(2) is bonded to one O(1), one O(10), one O(11), one O(13), and two equivalent O(2) atoms to form WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with three equivalent W(4)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-22°. In the third W site, W(3) is bonded to one O(16), one O(4), one O(6), one O(7), and two equivalent O(15) atoms to form WO6 octahedra that share corners with two equivalent W(3)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-31°. In the fourth W site, W(4) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(9) atom to form WO6 octahedra that share corners with three equivalent W(2)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 1-22°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(3), and one O(9) 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(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-27°. In the second P site, P(2) is bonded to one O(14), one O(16), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one W(3)O6 octahedra,  a cornercorner with one W(4)O6 octahedra, and corners with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-42°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one W(2), and one P(1) atom. In the second O site, O(2) is bonded in a linear geometry to two equivalent W(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one W(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one W(1), and one W(3) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to one W(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one W(1) and one W(3) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(1), one W(1), and one W(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one W(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one W(4), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one W(2) and one W(4) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one W(2) and one W(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one W(4) and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Li(2), one W(2), and one W(4) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one W(4) and one P(2) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to two equivalent W(3) atoms. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one W(3), and one P(2) atom.
LiP(WO4)2 crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 5-coordinate geometry to one O(16), one O(3), one O(4), one O(7), and one O(9) atom. The Li(1)-O(16) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.30 Å. The Li(1)-O(4) bond length is 2.27 Å. The Li(1)-O(7) bond length is 2.40 Å. The Li(1)-O(9) bond length is 2.43 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(1), one O(13), and one O(8) atom. The Li(2)-O(1) bond length is 2.03 Å. The Li(2)-O(13) bond length is 2.09 Å. The Li(2)-O(8) bond length is 2.11 Å. There are four inequivalent W sites. In the first W site, W(1) is bonded to one O(3), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form WO6 octahedra that share corners with three equivalent W(3)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 1-31°. The W(1)-O(3) bond length is 2.07 Å. The W(1)-O(4) bond length is 1.92 Å. The W(1)-O(5) bond length is 2.13 Å. The W(1)-O(6) bond length is 1.84 Å. The W(1)-O(7) bond length is 1.97 Å. The W(1)-O(8) bond length is 2.17 Å. In the second W site, W(2) is bonded to one O(1), one O(10), one O(11), one O(13), and two equivalent O(2) atoms to form WO6 octahedra that share corners with two equivalent W(2)O6 octahedra, corners with three equivalent W(4)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-22°. The W(2)-O(1) bond length is 2.11 Å. The W(2)-O(10) bond length is 1.93 Å. The W(2)-O(11) bond length is 2.02 Å. The W(2)-O(13) bond length is 2.01 Å. There is one shorter (1.86 Å) and one longer (2.01 Å) W(2)-O(2) bond length. In the third W site, W(3) is bonded to one O(16), one O(4), one O(6), one O(7), and two equivalent O(15) atoms to form WO6 octahedra that share corners with two equivalent W(3)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 1-31°. The W(3)-O(16) bond length is 2.13 Å. The W(3)-O(4) bond length is 2.03 Å. The W(3)-O(6) bond length is 2.02 Å. The W(3)-O(7) bond length is 1.94 Å. There is one shorter (1.86 Å) and one longer (2.02 Å) W(3)-O(15) bond length. In the fourth W site, W(4) is bonded to one O(10), one O(11), one O(12), one O(13), one O(14), and one O(9) atom to form WO6 octahedra that share corners with three equivalent W(2)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 1-22°. The W(4)-O(10) bond length is 1.96 Å. The W(4)-O(11) bond length is 1.83 Å. The W(4)-O(12) bond length is 2.15 Å. The W(4)-O(13) bond length is 1.91 Å. The W(4)-O(14) bond length is 2.10 Å. The W(4)-O(9) bond length is 2.09 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(12), one O(3), and one O(9) 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(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-27°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(12) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(9) bond length is 1.54 Å. In the second P site, P(2) is bonded to one O(14), one O(16), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one W(3)O6 octahedra,  a cornercorner with one W(4)O6 octahedra, and corners with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-42°. The P(2)-O(14) bond length is 1.54 Å. The P(2)-O(16) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(8) bond length is 1.57 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one W(2), and one P(1) atom. In the second O site, O(2) is bonded in a linear geometry to two equivalent W(2) atoms. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one W(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one W(1), and one W(3) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to one W(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to one W(1) and one W(3) atom. In the seventh O site, O(7) is bonded in a T-shaped geometry to one Li(1), one W(1), and one W(3) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(2), one W(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted T-shaped geometry to one Li(1), one W(4), and one P(1) atom. In the tenth O site, O(10) is bonded in a distorted linear geometry to one W(2) and one W(4) atom. In the eleventh O site, O(11) is bonded in a linear geometry to one W(2) and one W(4) atom. In the twelfth O site, O(12) is bonded in a distorted bent 150 degrees geometry to one W(4) and one P(1) atom. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Li(2), one W(2), and one W(4) atom. In the fourteenth O site, O(14) is bonded in a distorted bent 150 degrees geometry to one W(4) and one P(2) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to two equivalent W(3) atoms. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one W(3), and one P(2) atom.