Li3VSi4(HO6)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(12), one O(2), and one O(7) atom. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(4), one O(5), and one O(7) atom. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(12), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent Si(4)O4 tetrahedra. In the second V site, V(2) is bonded to two equivalent O(11), two equivalent O(12), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and corners with two equivalent Si(4)O4 tetrahedra. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-54°. In the second Si site, Si(2) is bonded to one O(10), one O(2), one O(4), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. In the third Si site, Si(3) is bonded to one O(11), one O(3), one O(6), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. In the fourth Si site, Si(4) is bonded to one O(10), one O(12), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-46°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(5) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(5) atom. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(1), and one Si(1) atom to form distorted corner-sharing OLi2VSi tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one H(1), and one H(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one V(2), and one Si(1) atom to form distorted corner-sharing OLi2VSi tetrahedra. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one Si(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Si(3) and one Si(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Si(2) and one Si(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one Si(3) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(2), and one Si(4) atom.
Li3VSi4(HO6)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(12), one O(2), and one O(7) atom. The Li(1)-O(1) bond length is 2.25 Å. The Li(1)-O(12) bond length is 2.33 Å. The Li(1)-O(2) bond length is 2.05 Å. The Li(1)-O(7) bond length is 2.02 Å. In the second Li site, Li(2) is bonded in a 3-coordinate geometry to one O(4), one O(5), and one O(7) atom. The Li(2)-O(4) bond length is 2.12 Å. The Li(2)-O(5) bond length is 1.93 Å. The Li(2)-O(7) bond length is 2.16 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(11), one O(12), and one O(8) atom. The Li(3)-O(1) bond length is 2.08 Å. The Li(3)-O(11) bond length is 2.00 Å. The Li(3)-O(12) bond length is 2.17 Å. The Li(3)-O(8) bond length is 2.15 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(8) atoms to form VO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent Si(4)O4 tetrahedra. Both V(1)-O(1) bond lengths are 2.05 Å. Both V(1)-O(2) bond lengths are 2.09 Å. Both V(1)-O(8) bond lengths are 1.99 Å. In the second V site, V(2) is bonded to two equivalent O(11), two equivalent O(12), and two equivalent O(7) atoms to form VO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and corners with two equivalent Si(4)O4 tetrahedra. Both V(2)-O(11) bond lengths are 2.12 Å. Both V(2)-O(12) bond lengths are 1.99 Å. Both V(2)-O(7) bond lengths are 2.06 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(3), one O(4), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-54°. The Si(1)-O(1) bond length is 1.61 Å. The Si(1)-O(3) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.69 Å. The Si(1)-O(7) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(10), one O(2), one O(4), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 58°. The Si(2)-O(10) bond length is 1.64 Å. The Si(2)-O(2) bond length is 1.61 Å. The Si(2)-O(4) bond length is 1.67 Å. The Si(2)-O(6) bond length is 1.64 Å. In the third Si site, Si(3) is bonded to one O(11), one O(3), one O(6), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 60°. The Si(3)-O(11) bond length is 1.60 Å. The Si(3)-O(3) bond length is 1.63 Å. The Si(3)-O(6) bond length is 1.65 Å. The Si(3)-O(9) bond length is 1.67 Å. In the fourth Si site, Si(4) is bonded to one O(10), one O(12), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 28-46°. The Si(4)-O(10) bond length is 1.64 Å. The Si(4)-O(12) bond length is 1.63 Å. The Si(4)-O(8) bond length is 1.61 Å. The Si(4)-O(9) bond length is 1.68 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(5) atom. The H(1)-O(5) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(5) atom. The H(2)-O(5) bond length is 0.98 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), one V(1), and one Si(1) atom to form distorted corner-sharing OLi2VSi tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one V(1), and one Si(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one H(1), and one H(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the seventh O site, O(7) is bonded to one Li(1), one Li(2), one V(2), and one Si(1) atom to form distorted corner-sharing OLi2VSi tetrahedra. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(3), one V(1), and one Si(4) atom. In the ninth O site, O(9) is bonded in a bent 120 degrees geometry to one Si(3) and one Si(4) atom. In the tenth O site, O(10) is bonded in a distorted bent 150 degrees geometry to one Si(2) and one Si(4) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one V(2), and one Si(3) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(3), one V(2), and one Si(4) atom.