Li3SiBiO5 crystallizes in the orthorhombic Pna2_1 space group. There are three 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(5) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Si(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 trigonal pyramids. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, and corners with two equivalent Li(3)O4 trigonal pyramids. 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 three equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, and corners with three equivalent Li(3)O4 trigonal pyramids. Bi(1) is bonded in a 4-coordinate geometry to one O(4), one O(5), and two equivalent O(1) atoms. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent Bi(1) atoms to form distorted OLi2Bi2 tetrahedra that share corners with two equivalent O(1)Li2Bi2 tetrahedra,  a cornercorner with one O(3)Li3Si trigonal pyramid, corners with two equivalent O(2)Li3Si trigonal pyramids, corners with three equivalent O(5)Li2SiBi trigonal pyramids, and edges with two equivalent O(4)Li2SiBi trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one Si(1) atom to form OLi3Si trigonal pyramids that share corners with two equivalent O(1)Li2Bi2 tetrahedra, corners with three equivalent O(4)Li2SiBi trigonal pyramids, corners with three equivalent O(5)Li2SiBi trigonal pyramids, and corners with four equivalent O(3)Li3Si trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and one Si(1) atom to form OLi3Si trigonal pyramids that share  a cornercorner with one O(1)Li2Bi2 tetrahedra,  a cornercorner with one O(4)Li2SiBi trigonal pyramid, corners with two equivalent O(3)Li3Si trigonal pyramids, corners with four equivalent O(5)Li2SiBi trigonal pyramids, and corners with four equivalent O(2)Li3Si trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Si(1), and one Bi(1) atom to form distorted OLi2SiBi trigonal pyramids that share  a cornercorner with one O(3)Li3Si trigonal pyramid, corners with two equivalent O(4)Li2SiBi trigonal pyramids, corners with three equivalent O(2)Li3Si trigonal pyramids, edges with two equivalent O(1)Li2Bi2 tetrahedra, and  an edgeedge with one O(5)Li2SiBi trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Si(1), and one Bi(1) atom to form distorted OLi2SiBi trigonal pyramids that share corners with three equivalent O(1)Li2Bi2 tetrahedra, corners with three equivalent O(2)Li3Si trigonal pyramids, corners with four equivalent O(3)Li3Si trigonal pyramids, and  an edgeedge with one O(4)Li2SiBi trigonal pyramid.
Li3SiBiO5 crystallizes in the orthorhombic Pna2_1 space group. There are three 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(5) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Si(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, and corners with two equivalent Li(3)O4 trigonal pyramids. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(2) bond length is 2.03 Å. The Li(1)-O(3) bond length is 2.16 Å. The Li(1)-O(5) bond length is 2.01 Å. In the second Li site, Li(2) is bonded to one O(2), one O(5), and two equivalent O(3) atoms to form LiO4 tetrahedra that share corners with two equivalent Li(2)O4 tetrahedra, corners with four equivalent Li(1)O4 tetrahedra, corners with four equivalent Si(1)O4 tetrahedra, and  a cornercorner with one Li(3)O4 trigonal pyramid. The Li(2)-O(2) bond length is 2.07 Å. The Li(2)-O(5) bond length is 1.99 Å. There is one shorter (2.01 Å) and one longer (2.05 Å) Li(2)-O(3) bond length. In the third Li site, Li(3) is bonded to one O(1), one O(2), and two equivalent O(4) atoms to form LiO4 trigonal pyramids that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, and corners with two equivalent Li(3)O4 trigonal pyramids. The Li(3)-O(1) bond length is 2.00 Å. The Li(3)-O(2) bond length is 1.96 Å. There is one shorter (2.12 Å) and one longer (2.14 Å) Li(3)-O(4) bond length. 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 three equivalent Li(1)O4 tetrahedra, corners with four equivalent Li(2)O4 tetrahedra, and corners with three equivalent Li(3)O4 trigonal pyramids. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(4) bond length is 1.72 Å. The Si(1)-O(5) bond length is 1.67 Å. Bi(1) is bonded in a 4-coordinate geometry to one O(4), one O(5), and two equivalent O(1) atoms. The Bi(1)-O(4) bond length is 2.33 Å. The Bi(1)-O(5) bond length is 2.28 Å. There is one shorter (2.16 Å) and one longer (2.25 Å) Bi(1)-O(1) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(3), and two equivalent Bi(1) atoms to form distorted OLi2Bi2 tetrahedra that share corners with two equivalent O(1)Li2Bi2 tetrahedra,  a cornercorner with one O(3)Li3Si trigonal pyramid, corners with two equivalent O(2)Li3Si trigonal pyramids, corners with three equivalent O(5)Li2SiBi trigonal pyramids, and edges with two equivalent O(4)Li2SiBi trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), and one Si(1) atom to form OLi3Si trigonal pyramids that share corners with two equivalent O(1)Li2Bi2 tetrahedra, corners with three equivalent O(4)Li2SiBi trigonal pyramids, corners with three equivalent O(5)Li2SiBi trigonal pyramids, and corners with four equivalent O(3)Li3Si trigonal pyramids. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(2), and one Si(1) atom to form OLi3Si trigonal pyramids that share  a cornercorner with one O(1)Li2Bi2 tetrahedra,  a cornercorner with one O(4)Li2SiBi trigonal pyramid, corners with two equivalent O(3)Li3Si trigonal pyramids, corners with four equivalent O(5)Li2SiBi trigonal pyramids, and corners with four equivalent O(2)Li3Si trigonal pyramids. In the fourth O site, O(4) is bonded to two equivalent Li(3), one Si(1), and one Bi(1) atom to form distorted OLi2SiBi trigonal pyramids that share  a cornercorner with one O(3)Li3Si trigonal pyramid, corners with two equivalent O(4)Li2SiBi trigonal pyramids, corners with three equivalent O(2)Li3Si trigonal pyramids, edges with two equivalent O(1)Li2Bi2 tetrahedra, and  an edgeedge with one O(5)Li2SiBi trigonal pyramid. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one Si(1), and one Bi(1) atom to form distorted OLi2SiBi trigonal pyramids that share corners with three equivalent O(1)Li2Bi2 tetrahedra, corners with three equivalent O(2)Li3Si trigonal pyramids, corners with four equivalent O(3)Li3Si trigonal pyramids, and  an edgeedge with one O(4)Li2SiBi trigonal pyramid.