LiVSi4(HO6)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(10), one O(11), one O(12), one O(5), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. There are two 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(8) atoms to form VO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra, and corners with two equivalent Li(1)O5 trigonal bipyramids. 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, corners with two equivalent Si(4)O4 tetrahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), 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 36-37°. In the second Si site, Si(2) is bonded to one O(1), one O(10), one O(3), 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,  a cornercorner with one Si(4)O4 tetrahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. In the third Si site, Si(3) is bonded to one O(11), one O(2), 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,  a cornercorner with one Si(4)O4 tetrahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 48°. 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,  a cornercorner with one Si(3)O4 tetrahedra,  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 36-42°. 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 in a bent 120 degrees geometry to one V(1) and one Si(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one Si(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), 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 in a bent 150 degrees geometry to one V(2) and one Si(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), 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 3-coordinate geometry to one Li(1), one Si(2), and one Si(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Si(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Si(4) atom.
LiVSi4(HO6)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(10), one O(11), one O(12), one O(5), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and  an edgeedge with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles are 62°. The Li(1)-O(10) bond length is 2.25 Å. The Li(1)-O(11) bond length is 2.04 Å. The Li(1)-O(12) bond length is 2.12 Å. The Li(1)-O(5) bond length is 1.97 Å. The Li(1)-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(4), 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, corners with two equivalent Si(4)O4 tetrahedra, and corners with two equivalent Li(1)O5 trigonal bipyramids. Both V(1)-O(1) bond lengths are 1.93 Å. Both V(1)-O(4) bond lengths are 1.87 Å. Both V(1)-O(8) bond lengths are 1.91 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, corners with two equivalent Si(4)O4 tetrahedra, and edges with two equivalent Li(1)O5 trigonal bipyramids. Both V(2)-O(11) bond lengths are 1.92 Å. Both V(2)-O(12) bond lengths are 1.91 Å. Both V(2)-O(7) bond lengths are 1.85 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), 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 36-37°. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.65 Å. The Si(1)-O(4) bond length is 1.65 Å. The Si(1)-O(7) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(1), one O(10), one O(3), 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,  a cornercorner with one Si(4)O4 tetrahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 53°. The Si(2)-O(1) bond length is 1.63 Å. The Si(2)-O(10) bond length is 1.65 Å. The Si(2)-O(3) bond length is 1.64 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(2), 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,  a cornercorner with one Si(4)O4 tetrahedra, and  a cornercorner with one Li(1)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 48°. The Si(3)-O(11) bond length is 1.63 Å. The Si(3)-O(2) bond length is 1.63 Å. The Si(3)-O(6) bond length is 1.64 Å. The Si(3)-O(9) bond length is 1.63 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,  a cornercorner with one Si(3)O4 tetrahedra,  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 36-42°. The Si(4)-O(10) bond length is 1.65 Å. The Si(4)-O(12) bond length is 1.64 Å. The Si(4)-O(8) bond length is 1.63 Å. The Si(4)-O(9) bond length is 1.63 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 0.97 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one V(1) and one Si(2) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one V(1) and one Si(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), 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 in a bent 150 degrees geometry to one V(2) and one Si(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), 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 3-coordinate geometry to one Li(1), one Si(2), and one Si(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Si(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one V(2), and one Si(4) atom.