Li2V2Si5O13 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(10), one O(12), and one O(13) atom. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(10), one O(5), and one O(8) atom. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(12), one O(7), one O(8), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. In the second V site, V(2) is bonded to one O(10), one O(2), one O(7), one O(8), and two equivalent O(12) atoms to form distorted VO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. There are five 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(5) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, and  a cornercorner with one Si(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-71°. In the second Si site, Si(2) is bonded to one O(1), one O(11), one O(13), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(4)O4 tetrahedra, and corners with two equivalent Si(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. In the third Si site, Si(3) is bonded to one O(4), one O(7), one O(8), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-63°. In the fourth Si site, Si(4) is bonded to one O(12), one O(13), one O(5), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent 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(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-72°. In the fifth Si site, Si(5) is bonded to one O(10), one O(11), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one Si(2) atom. In the second O site, O(2) is bonded to one V(2), two equivalent V(1), and one Si(1) atom to form distorted OV3Si tetrahedra that share corners with three equivalent O(8)LiV2Si trigonal pyramids and  an edgeedge with one O(2)V3Si tetrahedra. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(5) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Si(1), and one Si(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(5) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Si(3) atom. In the eighth O site, O(8) is bonded to one Li(2), one V(1), one V(2), and one Si(3) atom to form distorted corner-sharing OLiV2Si trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Si(3) and one Si(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one Si(5) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Si(2) and one Si(5) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Li(1), one V(1), two equivalent V(2), and one Si(4) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Li(1), one Si(2), and one Si(4) atom.
Li2V2Si5O13 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(1), one O(10), one O(12), and one O(13) atom. The Li(1)-O(1) bond length is 1.86 Å. The Li(1)-O(10) bond length is 1.82 Å. The Li(1)-O(12) bond length is 2.55 Å. The Li(1)-O(13) bond length is 1.86 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(10), one O(5), and one O(8) atom. The Li(2)-O(1) bond length is 2.07 Å. The Li(2)-O(10) bond length is 2.06 Å. The Li(2)-O(5) bond length is 2.12 Å. The Li(2)-O(8) bond length is 1.93 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(12), one O(7), one O(8), and two equivalent O(2) atoms to form VO6 octahedra that share  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra,  an edgeedge with one V(1)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The V(1)-O(1) bond length is 2.19 Å. The V(1)-O(12) bond length is 2.30 Å. The V(1)-O(7) bond length is 2.25 Å. The V(1)-O(8) bond length is 2.35 Å. There is one shorter (2.24 Å) and one longer (2.31 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded to one O(10), one O(2), one O(7), one O(8), and two equivalent O(12) atoms to form distorted VO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra,  an edgeedge with one V(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The V(2)-O(10) bond length is 2.14 Å. The V(2)-O(2) bond length is 2.37 Å. The V(2)-O(7) bond length is 2.23 Å. The V(2)-O(8) bond length is 2.31 Å. There is one shorter (2.24 Å) and one longer (2.55 Å) V(2)-O(12) bond length. There are five 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(5) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra, corners with two equivalent V(1)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, and  a cornercorner with one Si(5)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-71°. 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 1.63 Å. The Si(1)-O(5) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to one O(1), one O(11), one O(13), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one Si(4)O4 tetrahedra, and corners with two equivalent Si(5)O4 tetrahedra. The corner-sharing octahedral tilt angles are 43°. The Si(2)-O(1) bond length is 1.60 Å. The Si(2)-O(11) bond length is 1.64 Å. The Si(2)-O(13) bond length is 1.68 Å. The Si(2)-O(6) bond length is 1.60 Å. In the third Si site, Si(3) is bonded to one O(4), one O(7), one O(8), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent V(1)O6 octahedra, corners with two equivalent V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 56-63°. The Si(3)-O(4) bond length is 1.66 Å. The Si(3)-O(7) bond length is 1.62 Å. The Si(3)-O(8) bond length is 1.64 Å. The Si(3)-O(9) bond length is 1.67 Å. In the fourth Si site, Si(4) is bonded to one O(12), one O(13), one O(5), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one V(1)O6 octahedra, corners with two equivalent 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(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-72°. The Si(4)-O(12) bond length is 1.63 Å. The Si(4)-O(13) bond length is 1.68 Å. The Si(4)-O(5) bond length is 1.64 Å. The Si(4)-O(9) bond length is 1.62 Å. In the fifth Si site, Si(5) is bonded to one O(10), one O(11), one O(3), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 40°. The Si(5)-O(10) bond length is 1.60 Å. The Si(5)-O(11) bond length is 1.65 Å. The Si(5)-O(3) bond length is 1.66 Å. The Si(5)-O(6) bond length is 1.60 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(1), and one Si(2) atom. In the second O site, O(2) is bonded to one V(2), two equivalent V(1), and one Si(1) atom to form distorted OV3Si tetrahedra that share corners with three equivalent O(8)LiV2Si trigonal pyramids and  an edgeedge with one O(2)V3Si tetrahedra. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(5) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(2), one Si(1), and one Si(4) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(5) atom. In the seventh O site, O(7) is bonded in a trigonal planar geometry to one V(1), one V(2), and one Si(3) atom. In the eighth O site, O(8) is bonded to one Li(2), one V(1), one V(2), and one Si(3) atom to form distorted corner-sharing OLiV2Si trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Si(3) and one Si(4) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one V(2), and one Si(5) atom. In the eleventh O site, O(11) is bonded in a distorted bent 150 degrees geometry to one Si(2) and one Si(5) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Li(1), one V(1), two equivalent V(2), and one Si(4) atom. In the thirteenth O site, O(13) is bonded in a trigonal planar geometry to one Li(1), one Si(2), and one Si(4) atom.