LiMo2PO8 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(11), one O(12), one O(13), one O(14), and one O(4) atom. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(2), one O(3), and one O(9) atom. There are four inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(15), one O(2), one O(3), one O(7), and two equivalent O(16) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with three equivalent Mo(4)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 3-22°. In the second Mo site, Mo(2) is bonded to one O(11), one O(13), one O(6), one O(8), and two equivalent O(1) atoms to form MoO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with three equivalent Mo(3)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-30°. In the third Mo site, Mo(3) is bonded to one O(13), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form MoO6 octahedra that share corners with three equivalent Mo(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 2-30°. In the fourth Mo site, Mo(4) is bonded to one O(10), one O(12), one O(14), one O(15), one O(2), and one O(7) atom to form distorted MoO6 octahedra that share corners with three equivalent Mo(1)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 3-22°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one Mo(4)O6 octahedra, and corners with two equivalent Mo(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-44°. In the second P site, P(2) is bonded to one O(12), one O(14), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(3)O6 octahedra, and corners with two equivalent Mo(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-30°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent Mo(2) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Mo(1), and one Mo(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Mo(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Mo(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to one Mo(3) and one P(1) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Mo(2) and one Mo(3) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Mo(1) and one Mo(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Mo(2) and one Mo(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Mo(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(4) and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Mo(4), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one Mo(3) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(1), one Mo(4), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Mo(1) and one Mo(4) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to two equivalent Mo(1) atoms.
LiMo2PO8 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(11), one O(12), one O(13), one O(14), and one O(4) atom. The Li(1)-O(11) bond length is 2.04 Å. The Li(1)-O(12) bond length is 2.43 Å. The Li(1)-O(13) bond length is 2.52 Å. The Li(1)-O(14) bond length is 2.23 Å. The Li(1)-O(4) bond length is 2.29 Å. In the second Li site, Li(2) is bonded in a distorted trigonal planar geometry to one O(2), one O(3), and one O(9) atom. The Li(2)-O(2) bond length is 2.10 Å. The Li(2)-O(3) bond length is 2.03 Å. The Li(2)-O(9) bond length is 2.02 Å. There are four inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to one O(15), one O(2), one O(3), one O(7), and two equivalent O(16) atoms to form MoO6 octahedra that share corners with two equivalent Mo(1)O6 octahedra, corners with three equivalent Mo(4)O6 octahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 3-22°. The Mo(1)-O(15) bond length is 1.91 Å. The Mo(1)-O(2) bond length is 2.01 Å. The Mo(1)-O(3) bond length is 2.09 Å. The Mo(1)-O(7) bond length is 2.04 Å. There is one shorter (1.83 Å) and one longer (2.01 Å) Mo(1)-O(16) bond length. In the second Mo site, Mo(2) is bonded to one O(11), one O(13), one O(6), one O(8), and two equivalent O(1) atoms to form MoO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with three equivalent Mo(3)O6 octahedra, and  a cornercorner with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 2-30°. The Mo(2)-O(11) bond length is 2.11 Å. The Mo(2)-O(13) bond length is 2.01 Å. The Mo(2)-O(6) bond length is 2.04 Å. The Mo(2)-O(8) bond length is 1.91 Å. There is one shorter (1.83 Å) and one longer (2.05 Å) Mo(2)-O(1) bond length. In the third Mo site, Mo(3) is bonded to one O(13), one O(4), one O(5), one O(6), one O(8), and one O(9) atom to form MoO6 octahedra that share corners with three equivalent Mo(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 2-30°. The Mo(3)-O(13) bond length is 1.89 Å. The Mo(3)-O(4) bond length is 2.09 Å. The Mo(3)-O(5) bond length is 2.15 Å. The Mo(3)-O(6) bond length is 1.80 Å. The Mo(3)-O(8) bond length is 1.96 Å. The Mo(3)-O(9) bond length is 2.18 Å. In the fourth Mo site, Mo(4) is bonded to one O(10), one O(12), one O(14), one O(15), one O(2), and one O(7) atom to form distorted MoO6 octahedra that share corners with three equivalent Mo(1)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 3-22°. The Mo(4)-O(10) bond length is 2.09 Å. The Mo(4)-O(12) bond length is 2.18 Å. The Mo(4)-O(14) bond length is 2.12 Å. The Mo(4)-O(15) bond length is 1.95 Å. The Mo(4)-O(2) bond length is 1.89 Å. The Mo(4)-O(7) bond length is 1.80 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(11), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(2)O6 octahedra,  a cornercorner with one Mo(4)O6 octahedra, and corners with two equivalent Mo(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-44°. The P(1)-O(10) bond length is 1.55 Å. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.51 Å. The P(1)-O(9) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(12), one O(14), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(3)O6 octahedra, and corners with two equivalent Mo(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-30°. The P(2)-O(12) bond length is 1.54 Å. The P(2)-O(14) bond length is 1.53 Å. The P(2)-O(3) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.54 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent Mo(2) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(2), one Mo(1), and one Mo(4) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Mo(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Mo(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted linear geometry to one Mo(3) and one P(1) atom. In the sixth O site, O(6) is bonded in a linear geometry to one Mo(2) and one Mo(3) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Mo(1) and one Mo(4) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Mo(2) and one Mo(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(2), one Mo(3), and one P(1) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(4) and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(1), one Mo(4), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one Mo(3) atom. In the fourteenth O site, O(14) is bonded in a distorted T-shaped geometry to one Li(1), one Mo(4), and one P(2) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Mo(1) and one Mo(4) atom. In the sixteenth O site, O(16) is bonded in a linear geometry to two equivalent Mo(1) atoms.