LiV2P4(HO8)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one O(1), one O(13), one O(15), one O(16), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)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 V(2)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 77°. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(14), one O(15), one O(2), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share  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, and  a cornercorner with one Li(1)O5 trigonal bipyramid. In the second V site, V(2) is bonded to one O(10), one O(11), one O(13), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  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, and  an edgeedge with one Li(1)O5 trigonal bipyramid. There are four inequivalent P sites. In the first P site, 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  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 14-48°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 14-44°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-48°. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(16) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 21-50°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(5) atom. In the second H site, H(2) is bonded in a linear geometry to one O(12) and one O(16) atom. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Li(1), one P(1), and one H(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(2) and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one P(3) and one H(2) atom. In the thirteenth O site, O(13) is bonded in a T-shaped geometry to one Li(1), one V(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one P(4), and one H(2) atom.
LiV2P4(HO8)2 crystallizes in the monoclinic P2_1 space group. Li(1) is bonded to one O(1), one O(13), one O(15), one O(16), and one O(7) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)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 V(2)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 77°. The Li(1)-O(1) bond length is 1.93 Å. The Li(1)-O(13) bond length is 2.02 Å. The Li(1)-O(15) bond length is 1.99 Å. The Li(1)-O(16) bond length is 2.18 Å. The Li(1)-O(7) bond length is 2.13 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(14), one O(15), one O(2), one O(3), one O(8), and one O(9) atom to form VO6 octahedra that share  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, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The V(1)-O(14) bond length is 1.94 Å. The V(1)-O(15) bond length is 2.05 Å. The V(1)-O(2) bond length is 1.94 Å. The V(1)-O(3) bond length is 1.95 Å. The V(1)-O(8) bond length is 1.90 Å. The V(1)-O(9) bond length is 1.88 Å. In the second V site, V(2) is bonded to one O(10), one O(11), one O(13), one O(4), one O(6), and one O(7) atom to form VO6 octahedra that share  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, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The V(2)-O(10) bond length is 1.85 Å. The V(2)-O(11) bond length is 1.92 Å. The V(2)-O(13) bond length is 1.95 Å. The V(2)-O(4) bond length is 1.81 Å. The V(2)-O(6) bond length is 1.93 Å. The V(2)-O(7) bond length is 2.04 Å. There are four inequivalent P sites. In the first P site, 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  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 14-48°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.60 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 14-44°. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(12), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 12-48°. The P(3)-O(10) bond length is 1.59 Å. The P(3)-O(11) bond length is 1.57 Å. The P(3)-O(12) bond length is 1.50 Å. The P(3)-O(9) bond length is 1.54 Å. In the fourth P site, P(4) is bonded to one O(13), one O(14), one O(15), and one O(16) atom to form PO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Li(1)O5 trigonal bipyramid, and  an edgeedge with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 21-50°. The P(4)-O(13) bond length is 1.56 Å. The P(4)-O(14) bond length is 1.52 Å. The P(4)-O(15) bond length is 1.55 Å. The P(4)-O(16) bond length is 1.55 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a linear geometry to one O(1) and one O(5) atom. The H(1)-O(1) bond length is 1.43 Å. The H(1)-O(5) bond length is 1.05 Å. In the second H site, H(2) is bonded in a linear geometry to one O(12) and one O(16) atom. The H(2)-O(12) bond length is 1.35 Å. The H(2)-O(16) bond length is 1.09 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a trigonal non-coplanar geometry to one Li(1), one P(1), and one H(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one V(1) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a linear geometry to one V(2) and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 120 degrees geometry to one P(2) and one H(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one V(2) and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted T-shaped geometry to one Li(1), one V(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one V(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a linear geometry to one V(1) and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one V(2) and one P(3) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one V(2) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 120 degrees geometry to one P(3) and one H(2) atom. In the thirteenth O site, O(13) is bonded in a T-shaped geometry to one Li(1), one V(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a bent 150 degrees geometry to one V(1) and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Li(1), one P(4), and one H(2) atom.