LiSi6Bi9O26 crystallizes in the trigonal P3 space group. Li(1) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(2), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Bi(3)O6 pentagonal pyramid, corners with two equivalent Bi(1)O6 pentagonal pyramids, and  an edgeedge with one Bi(3)O6 pentagonal pyramid. In the second Si site, Si(2) is bonded to one O(4), one O(7), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Bi(1)O6 pentagonal pyramid, corners with two equivalent Bi(3)O6 pentagonal pyramids, and  an edgeedge with one Bi(1)O6 pentagonal pyramid. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(2), one O(6), one O(7), one O(8), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share corners with two equivalent Bi(1)O6 pentagonal pyramids, corners with four equivalent Bi(3)O6 pentagonal pyramids,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to three equivalent O(2), three equivalent O(3), and three equivalent O(4) atoms. In the third Bi site, Bi(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(7), and one O(8) atom to form distorted BiO6 pentagonal pyramids that share corners with two equivalent Bi(3)O6 pentagonal pyramids, corners with four equivalent Bi(1)O6 pentagonal pyramids,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to three equivalent O(10) and three equivalent O(9) atoms. In the fifth Bi site, Bi(5) is bonded in a 9-coordinate geometry to three equivalent O(10), three equivalent O(8), and three equivalent O(9) atoms. There are ten inequivalent O sites. In the first O site, O(9) is bonded in a distorted single-bond geometry to one Si(2), one Bi(1), one Bi(4), and one Bi(5) atom. In the second O site, O(10) is bonded in a distorted single-bond geometry to one Si(1), one Bi(4), and one Bi(5) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Si(1), one Bi(1), and one Bi(3) atom. In the fourth O site, O(2) is bonded in a distorted single-bond geometry to one Si(1), one Bi(1), one Bi(2), and one Bi(3) atom. In the fifth O site, O(3) is bonded in a distorted single-bond geometry to one Li(1), one Si(1), one Bi(2), and one Bi(3) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Si(2), and one Bi(2) atom. In the seventh O site, O(5) is bonded in a trigonal planar geometry to three equivalent Bi(3) atoms. In the eighth O site, O(6) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Si(2), one Bi(1), and one Bi(3) atom. In the tenth O site, O(8) is bonded in a distorted single-bond geometry to one Si(2), one Bi(1), one Bi(3), and one Bi(5) atom.
LiSi6Bi9O26 crystallizes in the trigonal P3 space group. Li(1) is bonded in a 6-coordinate geometry to three equivalent O(3) and three equivalent O(4) atoms. All Li(1)-O(3) bond lengths are 2.52 Å. All Li(1)-O(4) bond lengths are 2.28 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(2), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Bi(3)O6 pentagonal pyramid, corners with two equivalent Bi(1)O6 pentagonal pyramids, and  an edgeedge with one Bi(3)O6 pentagonal pyramid. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(10) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.67 Å. The Si(1)-O(3) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(4), one O(7), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Bi(1)O6 pentagonal pyramid, corners with two equivalent Bi(3)O6 pentagonal pyramids, and  an edgeedge with one Bi(1)O6 pentagonal pyramid. The Si(2)-O(4) bond length is 1.62 Å. The Si(2)-O(7) bond length is 1.66 Å. The Si(2)-O(8) bond length is 1.66 Å. The Si(2)-O(9) bond length is 1.66 Å. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), one O(2), one O(6), one O(7), one O(8), and one O(9) atom to form distorted BiO6 pentagonal pyramids that share corners with two equivalent Bi(1)O6 pentagonal pyramids, corners with four equivalent Bi(3)O6 pentagonal pyramids,  a cornercorner with one Si(2)O4 tetrahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.34 Å. The Bi(1)-O(2) bond length is 2.63 Å. The Bi(1)-O(6) bond length is 2.29 Å. The Bi(1)-O(7) bond length is 2.43 Å. The Bi(1)-O(8) bond length is 2.35 Å. The Bi(1)-O(9) bond length is 2.45 Å. In the second Bi site, Bi(2) is bonded in a 9-coordinate geometry to three equivalent O(2), three equivalent O(3), and three equivalent O(4) atoms. All Bi(2)-O(2) bond lengths are 2.81 Å. All Bi(2)-O(3) bond lengths are 2.70 Å. All Bi(2)-O(4) bond lengths are 2.34 Å. In the third Bi site, Bi(3) is bonded to one O(1), one O(2), one O(3), one O(5), one O(7), and one O(8) atom to form distorted BiO6 pentagonal pyramids that share corners with two equivalent Bi(3)O6 pentagonal pyramids, corners with four equivalent Bi(1)O6 pentagonal pyramids,  a cornercorner with one Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The Bi(3)-O(1) bond length is 2.36 Å. The Bi(3)-O(2) bond length is 2.33 Å. The Bi(3)-O(3) bond length is 2.42 Å. The Bi(3)-O(5) bond length is 2.30 Å. The Bi(3)-O(7) bond length is 2.41 Å. The Bi(3)-O(8) bond length is 2.63 Å. In the fourth Bi site, Bi(4) is bonded in a 6-coordinate geometry to three equivalent O(10) and three equivalent O(9) atoms. All Bi(4)-O(10) bond lengths are 2.36 Å. All Bi(4)-O(9) bond lengths are 2.48 Å. In the fifth Bi site, Bi(5) is bonded in a 9-coordinate geometry to three equivalent O(10), three equivalent O(8), and three equivalent O(9) atoms. All Bi(5)-O(10) bond lengths are 2.37 Å. All Bi(5)-O(8) bond lengths are 2.79 Å. All Bi(5)-O(9) bond lengths are 2.63 Å. There are ten inequivalent O sites. In the first O site, O(9) is bonded in a distorted single-bond geometry to one Si(2), one Bi(1), one Bi(4), and one Bi(5) atom. In the second O site, O(10) is bonded in a distorted single-bond geometry to one Si(1), one Bi(4), and one Bi(5) atom. In the third O site, O(1) is bonded in a 3-coordinate geometry to one Si(1), one Bi(1), and one Bi(3) atom. In the fourth O site, O(2) is bonded in a distorted single-bond geometry to one Si(1), one Bi(1), one Bi(2), and one Bi(3) atom. In the fifth O site, O(3) is bonded in a distorted single-bond geometry to one Li(1), one Si(1), one Bi(2), and one Bi(3) atom. In the sixth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Si(2), and one Bi(2) atom. In the seventh O site, O(5) is bonded in a trigonal planar geometry to three equivalent Bi(3) atoms. In the eighth O site, O(6) is bonded in a trigonal planar geometry to three equivalent Bi(1) atoms. In the ninth O site, O(7) is bonded in a 3-coordinate geometry to one Si(2), one Bi(1), and one Bi(3) atom. In the tenth O site, O(8) is bonded in a distorted single-bond geometry to one Si(2), one Bi(1), one Bi(3), and one Bi(5) atom.