Li2Cr2Si4O11 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 distorted see-saw-like geometry to one O(1), one O(2), one O(3), and one O(7) atom. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(6), and one O(9) atom. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(7), one O(8), one O(9), and two equivalent O(11) atoms to form distorted CrO6 octahedra that share  a cornercorner with one Cr(2)O5 square pyramid,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O5 square pyramids. In the second Cr site, Cr(2) is bonded to one O(11), one O(3), one O(7), one O(8), and one O(9) atom to form distorted CrO5 square pyramids that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 76°. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O5 square pyramid,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. In the second Si site, Si(2) is bonded to one O(10), one O(11), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O5 square pyramid,  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 range from 62-66°. In the third Si site, Si(3) is bonded to one O(2), one O(5), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O5 square pyramid,  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(6), one O(7), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O5 square pyramids,  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 51-70°. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Si(1), and one Si(3) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cr(2), and one Si(1) atom to form distorted edge-sharing OLi2CrSi trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Si(3), and one Si(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Cr(1), one Cr(2), and one Si(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one Si(3) atom. In the ninth O site, O(9) is bonded to one Li(2), one Cr(1), one Cr(2), and one Si(4) atom to form distorted edge-sharing OLiCr2Si trigonal pyramids. 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 4-coordinate geometry to one Cr(2), two equivalent Cr(1), and one Si(2) atom.
Li2Cr2Si4O11 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 distorted see-saw-like geometry to one O(1), one O(2), one O(3), and one O(7) atom. The Li(1)-O(1) bond length is 2.19 Å. The Li(1)-O(2) bond length is 2.25 Å. The Li(1)-O(3) bond length is 2.06 Å. The Li(1)-O(7) bond length is 2.03 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(6), and one O(9) atom. The Li(2)-O(1) bond length is 2.29 Å. The Li(2)-O(3) bond length is 2.01 Å. The Li(2)-O(4) bond length is 2.08 Å. The Li(2)-O(6) bond length is 2.25 Å. The Li(2)-O(9) bond length is 2.19 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to one O(1), one O(7), one O(8), one O(9), and two equivalent O(11) atoms to form distorted CrO6 octahedra that share  a cornercorner with one Cr(2)O5 square pyramid,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra,  an edgeedge with one Cr(1)O6 octahedra, and edges with two equivalent Cr(2)O5 square pyramids. The Cr(1)-O(1) bond length is 2.03 Å. The Cr(1)-O(7) bond length is 2.59 Å. The Cr(1)-O(8) bond length is 2.11 Å. The Cr(1)-O(9) bond length is 2.06 Å. There is one shorter (2.13 Å) and one longer (2.47 Å) Cr(1)-O(11) bond length. In the second Cr site, Cr(2) is bonded to one O(11), one O(3), one O(7), one O(8), and one O(9) atom to form distorted CrO5 square pyramids that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, corners with two equivalent Si(4)O4 tetrahedra, and edges with two equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 76°. The Cr(2)-O(11) bond length is 2.13 Å. The Cr(2)-O(3) bond length is 2.08 Å. The Cr(2)-O(7) bond length is 2.09 Å. The Cr(2)-O(8) bond length is 2.06 Å. The Cr(2)-O(9) bond length is 2.42 Å. There are four inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O5 square pyramid,  a cornercorner with one Si(2)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 3°. The Si(1)-O(1) bond length is 1.60 Å. The Si(1)-O(2) bond length is 1.68 Å. The Si(1)-O(3) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.69 Å. In the second Si site, Si(2) is bonded to one O(10), one O(11), one O(4), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O5 square pyramid,  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 range from 62-66°. The Si(2)-O(10) bond length is 1.64 Å. The Si(2)-O(11) bond length is 1.62 Å. The Si(2)-O(4) bond length is 1.65 Å. The Si(2)-O(5) bond length is 1.64 Å. In the third Si site, Si(3) is bonded to one O(2), one O(5), one O(6), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O5 square pyramid,  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(2) bond length is 1.65 Å. The Si(3)-O(5) bond length is 1.64 Å. The Si(3)-O(6) bond length is 1.65 Å. The Si(3)-O(8) bond length is 1.62 Å. In the fourth Si site, Si(4) is bonded to one O(10), one O(6), one O(7), and one O(9) atom to form SiO4 tetrahedra that share corners with two equivalent Cr(1)O6 octahedra, corners with two equivalent Cr(2)O5 square pyramids,  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 51-70°. The Si(4)-O(10) bond length is 1.68 Å. The Si(4)-O(6) bond length is 1.69 Å. The Si(4)-O(7) bond length is 1.62 Å. The Si(4)-O(9) bond length is 1.62 Å. There are eleven inequivalent O sites. In the first O site, O(1) is bonded in a see-saw-like geometry to one Li(1), one Li(2), one Cr(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Li(1), one Si(1), and one Si(3) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Cr(2), and one Si(1) atom to form distorted edge-sharing OLi2CrSi trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(2), one Si(1), and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(2), one Si(3), and one Si(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Li(1), one Cr(1), one Cr(2), and one Si(4) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Cr(1), one Cr(2), and one Si(3) atom. In the ninth O site, O(9) is bonded to one Li(2), one Cr(1), one Cr(2), and one Si(4) atom to form distorted edge-sharing OLiCr2Si trigonal pyramids. 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 4-coordinate geometry to one Cr(2), two equivalent Cr(1), and one Si(2) atom.