Li2Mn2Si5O13 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 4-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 rectangular see-saw-like geometry to one O(1), one O(10), one O(5), and one O(8) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(7), one O(8), and two equivalent O(2) atoms to form distorted MnO6 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,  a cornercorner with one Mn(2)O5 trigonal bipyramid,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O5 trigonal bipyramids. In the second Mn site, Mn(2) is bonded to one O(10), one O(12), one O(2), one O(7), and one O(8) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. 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 corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 59-71°. 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 Mn(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 46°. 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 Mn(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 51-64°. 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 Mn(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, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 52°. 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 Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Si(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one Si(1) atom. 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 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 Mn(1), one Mn(2), and one Si(3) atom. In the eighth O site, O(8) is bonded to one Li(2), one Mn(1), one Mn(2), and one Si(3) atom to form distorted edge-sharing OLiMn2Si trigonal pyramids. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Si(3) and one Si(4) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(2), one Mn(2), and one Si(5) atom to form distorted edge-sharing OLi2MnSi trigonal pyramids. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(5) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one Si(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Si(2), and one Si(4) atom.
Li2Mn2Si5O13 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 4-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 1.87 Å. The Li(1)-O(10) bond length is 1.86 Å. The Li(1)-O(12) bond length is 2.42 Å. The Li(1)-O(13) bond length is 1.92 Å. In the second Li site, Li(2) is bonded in a 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 2.03 Å. The Li(2)-O(10) bond length is 2.07 Å. The Li(2)-O(5) bond length is 2.09 Å. The Li(2)-O(8) bond length is 1.92 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(7), one O(8), and two equivalent O(2) atoms to form distorted MnO6 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,  a cornercorner with one Mn(2)O5 trigonal bipyramid,  an edgeedge with one Mn(1)O6 octahedra, and edges with two equivalent Mn(2)O5 trigonal bipyramids. The Mn(1)-O(1) bond length is 2.20 Å. The Mn(1)-O(12) bond length is 2.18 Å. The Mn(1)-O(7) bond length is 2.15 Å. The Mn(1)-O(8) bond length is 2.41 Å. There is one shorter (2.30 Å) and one longer (2.54 Å) Mn(1)-O(2) bond length. In the second Mn site, Mn(2) is bonded to one O(10), one O(12), one O(2), one O(7), and one O(8) atom to form distorted MnO5 trigonal bipyramids that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 61°. The Mn(2)-O(10) bond length is 2.12 Å. The Mn(2)-O(12) bond length is 2.23 Å. The Mn(2)-O(2) bond length is 2.26 Å. The Mn(2)-O(7) bond length is 2.15 Å. The Mn(2)-O(8) bond length is 2.40 Å. 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 corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 59-71°. The Si(1)-O(2) bond length is 1.62 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 1.67 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 Mn(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 46°. 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 1.61 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 Mn(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 51-64°. The Si(3)-O(4) bond length is 1.65 Å. The Si(3)-O(7) bond length is 1.63 Å. The Si(3)-O(8) bond length is 1.63 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 Mn(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, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles are 52°. The Si(4)-O(12) bond length is 1.62 Å. The Si(4)-O(13) bond length is 1.67 Å. The Si(4)-O(5) bond length is 1.65 Å. The Si(4)-O(9) bond length is 1.63 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 Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  a cornercorner with one Mn(2)O5 trigonal bipyramid. The Si(5)-O(10) bond length is 1.61 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 1.62 Å. There are thirteen inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one Si(2) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Mn(2), two equivalent Mn(1), and one Si(1) atom. 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 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 Mn(1), one Mn(2), and one Si(3) atom. In the eighth O site, O(8) is bonded to one Li(2), one Mn(1), one Mn(2), and one Si(3) atom to form distorted edge-sharing OLiMn2Si trigonal pyramids. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one Si(3) and one Si(4) atom. In the tenth O site, O(10) is bonded to one Li(1), one Li(2), one Mn(2), and one Si(5) atom to form distorted edge-sharing OLi2MnSi trigonal pyramids. In the eleventh O site, O(11) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(5) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one Si(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(1), one Si(2), and one Si(4) atom.