Li3P3(WO6)2 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-69°. There are two inequivalent W sites. In the first W site, W(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids, and edges with three equivalent Li(1)O4 trigonal pyramids. In the second W site, W(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form WO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and corners with three equivalent Li(1)O4 trigonal pyramids. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, and corners with four equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 24-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one W(1), and one P(1) atom to form distorted corner-sharing OLi2PW tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one W(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), 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(2) and one P(1) atom.
Li3P3(WO6)2 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 trigonal pyramids that share  a cornercorner with one W(1)O6 octahedra,  a cornercorner with one W(2)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, corners with two equivalent Li(1)O4 trigonal pyramids, and  an edgeedge with one W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 65-69°. The Li(1)-O(2) bond length is 1.98 Å. The Li(1)-O(3) bond length is 1.96 Å. There is one shorter (2.02 Å) and one longer (2.27 Å) Li(1)-O(1) bond length. There are two inequivalent W sites. In the first W site, W(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 trigonal pyramids, and edges with three equivalent Li(1)O4 trigonal pyramids. All W(1)-O(1) bond lengths are 2.18 Å. All W(1)-O(2) bond lengths are 2.17 Å. In the second W site, W(2) is bonded to three equivalent O(3) and three equivalent O(4) atoms to form WO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and corners with three equivalent Li(1)O4 trigonal pyramids. All W(2)-O(3) bond lengths are 2.20 Å. All W(2)-O(4) bond lengths are 2.13 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent W(1)O6 octahedra, corners with two equivalent W(2)O6 octahedra, and corners with four equivalent Li(1)O4 trigonal pyramids. The corner-sharing octahedral tilt angles range from 24-52°. The P(1)-O(1) bond length is 1.59 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one W(1), and one P(1) atom to form distorted corner-sharing OLi2PW tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one W(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), 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(2) and one P(1) atom.