Li2VPO4OH crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one H(1), one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. In the second Li site, Li(1) is bonded in a 7-coordinate geometry to one H(1), one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. In the third Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. In the fourth Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. In the second V site, V(2) is bonded to two O(1,1); two O(2,2); and two O(3,3) atoms to form VO6 octahedra that share corners with two V(1,1)O6 octahedra and corners with four P(1,1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-58°. In the third V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-54°. In the second P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-54°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one Li(1) and one O(1) atom. In the second H site, H(1) is bonded in a single-bond geometry to one Li(1) and one O(1) atom. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(2), one V(1), one V(2), and one H(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(2), one V(1), one V(2), and one H(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the seventh O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the eighth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the ninth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the tenth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom.
Li2VPO4OH crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 7-coordinate geometry to one H(1), one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. The Li(1)-H(1) bond length is 2.15 Å. The Li(1)-O(1) bond length is 2.14 Å. The Li(1)-O(2) bond length is 2.30 Å. The Li(1)-O(3) bond length is 2.02 Å. The Li(1)-O(5) bond length is 2.39 Å. There is one shorter (2.00 Å) and one longer (2.44 Å) Li(1)-O(4) bond length. In the second Li site, Li(1) is bonded in a 7-coordinate geometry to one H(1), one O(1), one O(2), one O(3), one O(5), and two equivalent O(4) atoms. The Li(1)-H(1) bond length is 2.16 Å. The Li(1)-O(1) bond length is 2.15 Å. The Li(1)-O(2) bond length is 2.29 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(5) bond length is 2.39 Å. There is one shorter (2.00 Å) and one longer (2.44 Å) Li(1)-O(4) bond length. In the third Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(2)-O(1) bond length is 1.96 Å. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(5) bond length is 1.97 Å. In the fourth Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(2), one O(3), and one O(5) atom. The Li(2)-O(1) bond length is 1.96 Å. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(3) bond length is 2.18 Å. The Li(2)-O(5) bond length is 1.97 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. Both V(1)-O(1) bond lengths are 2.19 Å. Both V(1)-O(4) bond lengths are 2.17 Å. Both V(1)-O(5) bond lengths are 2.20 Å. In the second V site, V(2) is bonded to two O(1,1); two O(2,2); and two O(3,3) atoms to form VO6 octahedra that share corners with two V(1,1)O6 octahedra and corners with four P(1,1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 57-58°. Both V(2)-O(1,1) bond lengths are 2.21 Å. Both V(2)-O(2,2) bond lengths are 2.21 Å. Both V(2)-O(3,3) bond lengths are 2.22 Å. In the third V site, V(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent V(2)O6 octahedra and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 57°. Both V(1)-O(1) bond lengths are 2.19 Å. Both V(1)-O(4) bond lengths are 2.17 Å. Both V(1)-O(5) bond lengths are 2.20 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-54°. 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 1.55 Å. The P(1)-O(5) bond length is 1.55 Å. In the second P site, P(1) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra and corners with two equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 36-54°. 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 1.55 Å. The P(1)-O(5) bond length is 1.55 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one Li(1) and one O(1) atom. The H(1)-O(1) bond length is 0.98 Å. In the second H site, H(1) is bonded in a single-bond geometry to one Li(1) and one O(1) atom. The H(1)-O(1) bond length is 0.98 Å. There are ten inequivalent O sites. In the first O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(2), one V(1), one V(2), and one H(1) atom. In the second O site, O(1) is bonded in a distorted single-bond geometry to one Li(1), one Li(2), one V(1), one V(2), and one H(1) atom. In the third O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the fourth O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the fifth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(2), and one P(1) atom. In the seventh O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the eighth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Li(1), one V(1), and one P(1) atom. In the ninth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom. In the tenth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one V(1), and one P(1) atom.