Li3Mo3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(13), one O(4), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Mo(3)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 55°. In the second Li site, Li(2) is bonded to one O(10), one O(15), one O(2), one O(5), and one O(6) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(2)O6 octahedra,  an edgeedge with one Mo(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. In the third Li site, Li(3) is bonded to one O(1), one O(12), one O(16), one O(3), and one O(4) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Mo(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Mo(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 59°. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(10), one O(14), one O(6), one O(7), and one O(9) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mo(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Mo(2)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. In the second Mo site, Mo(2) is bonded to one O(13), one O(15), one O(2), one O(5), one O(7), and one O(9) atom to form MoO6 octahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Mo(1)O5 square pyramid. In the third Mo site, Mo(3) is bonded to one O(1), one O(11), one O(14), one O(16), one O(3), and one O(8) atom to form MoO6 octahedra that share  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(15), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(3)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 37-51°. In the second P site, P(2) is bonded to one O(1), one O(16), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-55°. In the third P site, P(3) is bonded to one O(11), one O(12), one O(14), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Mo(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 35-55°. In the fourth P site, P(4) is bonded to one O(10), one O(13), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(3)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent Mo(1)O5 square pyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-54°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Mo(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Mo(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(3), one Mo(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Mo(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mo(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Mo(1), one Mo(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one Mo(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mo(1), one Mo(2), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(2), one Mo(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Mo(3), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Mo(1), one Mo(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(2), one Mo(2), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(3), one Mo(3), and one P(2) atom.
Li3Mo3(PO4)4 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(13), one O(4), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Mo(3)O6 octahedra,  an edgeedge with one P(4)O4 tetrahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 55°. The Li(1)-O(11) bond length is 2.04 Å. The Li(1)-O(12) bond length is 1.90 Å. The Li(1)-O(13) bond length is 2.29 Å. The Li(1)-O(4) bond length is 1.91 Å. The Li(1)-O(8) bond length is 2.23 Å. In the second Li site, Li(2) is bonded to one O(10), one O(15), one O(2), one O(5), and one O(6) atom to form distorted LiO5 square pyramids that share  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Mo(2)O6 octahedra,  an edgeedge with one Mo(1)O5 square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. The Li(2)-O(10) bond length is 2.06 Å. The Li(2)-O(15) bond length is 2.15 Å. The Li(2)-O(2) bond length is 2.15 Å. The Li(2)-O(5) bond length is 2.00 Å. The Li(2)-O(6) bond length is 1.95 Å. In the third Li site, Li(3) is bonded to one O(1), one O(12), one O(16), one O(3), and one O(4) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Mo(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Mo(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 59°. The Li(3)-O(1) bond length is 2.26 Å. The Li(3)-O(12) bond length is 1.99 Å. The Li(3)-O(16) bond length is 2.15 Å. The Li(3)-O(3) bond length is 2.10 Å. The Li(3)-O(4) bond length is 1.90 Å. There are three inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(10), one O(14), one O(6), one O(7), and one O(9) atom to form distorted MoO5 square pyramids that share  a cornercorner with one Mo(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Mo(2)O6 octahedra,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 56°. The Mo(1)-O(10) bond length is 2.06 Å. The Mo(1)-O(14) bond length is 2.09 Å. The Mo(1)-O(6) bond length is 2.07 Å. The Mo(1)-O(7) bond length is 2.13 Å. The Mo(1)-O(9) bond length is 2.10 Å. In the second Mo site, Mo(2) is bonded to one O(13), one O(15), one O(2), one O(5), one O(7), and one O(9) atom to form MoO6 octahedra that share  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid,  an edgeedge with one Li(2)O5 square pyramid, and  an edgeedge with one Mo(1)O5 square pyramid. The Mo(2)-O(13) bond length is 2.16 Å. The Mo(2)-O(15) bond length is 2.16 Å. The Mo(2)-O(2) bond length is 2.09 Å. The Mo(2)-O(5) bond length is 2.09 Å. The Mo(2)-O(7) bond length is 2.18 Å. The Mo(2)-O(9) bond length is 2.24 Å. In the third Mo site, Mo(3) is bonded to one O(1), one O(11), one O(14), one O(16), one O(3), and one O(8) atom to form MoO6 octahedra that share  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid,  an edgeedge with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Mo(3)-O(1) bond length is 2.08 Å. The Mo(3)-O(11) bond length is 2.17 Å. The Mo(3)-O(14) bond length is 2.25 Å. The Mo(3)-O(16) bond length is 2.10 Å. The Mo(3)-O(3) bond length is 2.14 Å. The Mo(3)-O(8) bond length is 2.15 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(15), one O(2), one O(3), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(3)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Mo(1)O5 square pyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(2)O5 square pyramid. The corner-sharing octahedral tilt angles range from 37-51°. The P(1)-O(15) bond length is 1.55 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(1), one O(16), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid,  a cornercorner with one Li(1)O5 trigonal bipyramid,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 39-55°. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(16) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(11), one O(12), one O(14), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Mo(3)O6 octahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, corners with two equivalent Li(1)O5 trigonal bipyramids, and  an edgeedge with one Mo(1)O5 square pyramid. The corner-sharing octahedral tilt angles range from 35-55°. The P(3)-O(11) bond length is 1.53 Å. The P(3)-O(12) bond length is 1.49 Å. The P(3)-O(14) bond length is 1.63 Å. The P(3)-O(7) bond length is 1.60 Å. In the fourth P site, P(4) is bonded to one O(10), one O(13), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(3)O6 octahedra, corners with two equivalent Mo(2)O6 octahedra,  a cornercorner with one Li(2)O5 square pyramid, corners with two equivalent Mo(1)O5 square pyramids, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 31-54°. The P(4)-O(10) bond length is 1.55 Å. The P(4)-O(13) bond length is 1.54 Å. The P(4)-O(8) bond length is 1.53 Å. The P(4)-O(9) bond length is 1.59 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(3), one Mo(3), and one P(2) atom. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Mo(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(3), one Mo(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Mo(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(2), one Mo(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Mo(1), one Mo(2), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(1), one Mo(3), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Mo(1), one Mo(2), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(2), one Mo(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Mo(3), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted T-shaped geometry to one Li(1), one Li(3), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Mo(1), one Mo(3), and one P(3) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Li(2), one Mo(2), and one P(1) atom. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to one Li(3), one Mo(3), and one P(2) atom.