Li4MnSi2O7 is Stannite-like structured and crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, and corners with three equivalent Si(1)O4 tetrahedra. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Mn(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with three equivalent Si(1)O4 tetrahedra. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and corners with three equivalent Mn(1)O4 tetrahedra. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Mn(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with three equivalent Si(2)O4 tetrahedra. Mn(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form MnO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with three equivalent Si(2)O4 tetrahedra. There are two 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 Mn(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with three equivalent Li(2)O4 tetrahedra. In the second Si site, Si(2) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, and corners with three equivalent Mn(1)O4 tetrahedra. There are seven inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), and one Si(1) atom to form distorted OLi3Si tetrahedra that share  a cornercorner with one O(6)Li2MnSi tetrahedra,  a cornercorner with one O(7)Li2MnSi tetrahedra, corners with two equivalent O(5)Li2MnSi tetrahedra, corners with two equivalent O(1)Li2Si2 tetrahedra, corners with three equivalent O(4)Li2MnSi tetrahedra, and corners with three equivalent O(2)Li3Si tetrahedra. In the second O site, O(4) is bonded to one Li(2), one Li(3), one Mn(1), and one Si(1) atom to form distorted OLi2MnSi tetrahedra that share  a cornercorner with one O(7)Li2MnSi tetrahedra,  a cornercorner with one O(1)Li2Si2 tetrahedra, corners with two equivalent O(6)Li2MnSi tetrahedra, corners with two equivalent O(2)Li3Si tetrahedra, corners with three equivalent O(5)Li2MnSi tetrahedra, and corners with three equivalent O(3)Li3Si tetrahedra. In the third O site, O(5) is bonded to one Li(2), one Li(3), one Mn(1), and one Si(2) atom to form distorted OLi2MnSi tetrahedra that share  a cornercorner with one O(1)Li2Si2 tetrahedra,  a cornercorner with one O(2)Li3Si tetrahedra, corners with two equivalent O(7)Li2MnSi tetrahedra, corners with two equivalent O(3)Li3Si tetrahedra, corners with three equivalent O(4)Li2MnSi tetrahedra, and corners with three equivalent O(6)Li2MnSi tetrahedra. In the fourth O site, O(6) is bonded to one Li(3), one Li(4), one Mn(1), and one Si(2) atom to form OLi2MnSi tetrahedra that share  a cornercorner with one O(2)Li3Si tetrahedra,  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(4)Li2MnSi tetrahedra, corners with two equivalent O(1)Li2Si2 tetrahedra, corners with three equivalent O(5)Li2MnSi tetrahedra, and corners with three equivalent O(7)Li2MnSi tetrahedra. In the fifth O site, O(7) is bonded to one Li(1), one Li(4), one Mn(1), and one Si(2) atom to form OLi2MnSi tetrahedra that share  a cornercorner with one O(4)Li2MnSi tetrahedra,  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(5)Li2MnSi tetrahedra, corners with two equivalent O(2)Li3Si tetrahedra, corners with three equivalent O(6)Li2MnSi tetrahedra, and corners with three equivalent O(1)Li2Si2 tetrahedra. In the sixth O site, O(1) is bonded to one Li(1), one Li(4), one Si(1), and one Si(2) atom to form OLi2Si2 tetrahedra that share  a cornercorner with one O(4)Li2MnSi tetrahedra,  a cornercorner with one O(5)Li2MnSi tetrahedra, corners with two equivalent O(6)Li2MnSi tetrahedra, corners with two equivalent O(3)Li3Si tetrahedra, corners with three equivalent O(7)Li2MnSi tetrahedra, and corners with three equivalent O(2)Li3Si tetrahedra. In the seventh O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), and one Si(1) atom to form OLi3Si tetrahedra that share  a cornercorner with one O(5)Li2MnSi tetrahedra,  a cornercorner with one O(6)Li2MnSi tetrahedra, corners with two equivalent O(4)Li2MnSi tetrahedra, corners with two equivalent O(7)Li2MnSi tetrahedra, corners with three equivalent O(1)Li2Si2 tetrahedra, and corners with three equivalent O(3)Li3Si tetrahedra.
Li4MnSi2O7 is Stannite-like structured and crystallizes in the monoclinic Cc space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(3)O4 tetrahedra,  a cornercorner with one Mn(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, and corners with three equivalent Si(1)O4 tetrahedra. The Li(1)-O(1) bond length is 2.23 Å. The Li(1)-O(2) bond length is 1.94 Å. The Li(1)-O(3) bond length is 1.94 Å. The Li(1)-O(7) bond length is 2.05 Å. In the second Li site, Li(2) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(4)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Mn(1)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with three equivalent Si(1)O4 tetrahedra. The Li(2)-O(2) bond length is 1.93 Å. The Li(2)-O(3) bond length is 1.97 Å. The Li(2)-O(4) bond length is 2.05 Å. The Li(2)-O(5) bond length is 2.02 Å. In the third Li site, Li(3) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(4)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and corners with three equivalent Mn(1)O4 tetrahedra. The Li(3)-O(3) bond length is 2.01 Å. The Li(3)-O(4) bond length is 2.03 Å. The Li(3)-O(5) bond length is 2.06 Å. The Li(3)-O(6) bond length is 2.07 Å. In the fourth Li site, Li(4) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Li(3)O4 tetrahedra, corners with two equivalent Mn(1)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with three equivalent Si(2)O4 tetrahedra. The Li(4)-O(1) bond length is 2.18 Å. The Li(4)-O(2) bond length is 1.94 Å. The Li(4)-O(6) bond length is 2.02 Å. The Li(4)-O(7) bond length is 1.98 Å. Mn(1) is bonded to one O(4), one O(5), one O(6), and one O(7) atom to form MnO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(2)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(3)O4 tetrahedra, and corners with three equivalent Si(2)O4 tetrahedra. The Mn(1)-O(4) bond length is 2.09 Å. The Mn(1)-O(5) bond length is 2.05 Å. The Mn(1)-O(6) bond length is 2.06 Å. The Mn(1)-O(7) bond length is 2.07 Å. There are two 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 Mn(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with two equivalent Li(4)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, and corners with three equivalent Li(2)O4 tetrahedra. The Si(1)-O(1) bond length is 1.74 Å. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.66 Å. In the second Si site, Si(2) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent Li(3)O4 tetrahedra, corners with three equivalent Li(4)O4 tetrahedra, and corners with three equivalent Mn(1)O4 tetrahedra. The Si(2)-O(1) bond length is 1.71 Å. The Si(2)-O(5) bond length is 1.64 Å. The Si(2)-O(6) bond length is 1.65 Å. The Si(2)-O(7) bond length is 1.64 Å. There are seven inequivalent O sites. In the first O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), and one Si(1) atom to form distorted OLi3Si tetrahedra that share  a cornercorner with one O(6)Li2MnSi tetrahedra,  a cornercorner with one O(7)Li2MnSi tetrahedra, corners with two equivalent O(5)Li2MnSi tetrahedra, corners with two equivalent O(1)Li2Si2 tetrahedra, corners with three equivalent O(4)Li2MnSi tetrahedra, and corners with three equivalent O(2)Li3Si tetrahedra. In the second O site, O(4) is bonded to one Li(2), one Li(3), one Mn(1), and one Si(1) atom to form distorted OLi2MnSi tetrahedra that share  a cornercorner with one O(7)Li2MnSi tetrahedra,  a cornercorner with one O(1)Li2Si2 tetrahedra, corners with two equivalent O(6)Li2MnSi tetrahedra, corners with two equivalent O(2)Li3Si tetrahedra, corners with three equivalent O(5)Li2MnSi tetrahedra, and corners with three equivalent O(3)Li3Si tetrahedra. In the third O site, O(5) is bonded to one Li(2), one Li(3), one Mn(1), and one Si(2) atom to form distorted OLi2MnSi tetrahedra that share  a cornercorner with one O(1)Li2Si2 tetrahedra,  a cornercorner with one O(2)Li3Si tetrahedra, corners with two equivalent O(7)Li2MnSi tetrahedra, corners with two equivalent O(3)Li3Si tetrahedra, corners with three equivalent O(4)Li2MnSi tetrahedra, and corners with three equivalent O(6)Li2MnSi tetrahedra. In the fourth O site, O(6) is bonded to one Li(3), one Li(4), one Mn(1), and one Si(2) atom to form OLi2MnSi tetrahedra that share  a cornercorner with one O(2)Li3Si tetrahedra,  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(4)Li2MnSi tetrahedra, corners with two equivalent O(1)Li2Si2 tetrahedra, corners with three equivalent O(5)Li2MnSi tetrahedra, and corners with three equivalent O(7)Li2MnSi tetrahedra. In the fifth O site, O(7) is bonded to one Li(1), one Li(4), one Mn(1), and one Si(2) atom to form OLi2MnSi tetrahedra that share  a cornercorner with one O(4)Li2MnSi tetrahedra,  a cornercorner with one O(3)Li3Si tetrahedra, corners with two equivalent O(5)Li2MnSi tetrahedra, corners with two equivalent O(2)Li3Si tetrahedra, corners with three equivalent O(6)Li2MnSi tetrahedra, and corners with three equivalent O(1)Li2Si2 tetrahedra. In the sixth O site, O(1) is bonded to one Li(1), one Li(4), one Si(1), and one Si(2) atom to form OLi2Si2 tetrahedra that share  a cornercorner with one O(4)Li2MnSi tetrahedra,  a cornercorner with one O(5)Li2MnSi tetrahedra, corners with two equivalent O(6)Li2MnSi tetrahedra, corners with two equivalent O(3)Li3Si tetrahedra, corners with three equivalent O(7)Li2MnSi tetrahedra, and corners with three equivalent O(2)Li3Si tetrahedra. In the seventh O site, O(2) is bonded to one Li(1), one Li(2), one Li(4), and one Si(1) atom to form OLi3Si tetrahedra that share  a cornercorner with one O(5)Li2MnSi tetrahedra,  a cornercorner with one O(6)Li2MnSi tetrahedra, corners with two equivalent O(4)Li2MnSi tetrahedra, corners with two equivalent O(7)Li2MnSi tetrahedra, corners with three equivalent O(1)Li2Si2 tetrahedra, and corners with three equivalent O(3)Li3Si tetrahedra.