Li5Bi(P2O7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(6), one O(8), and one O(9) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Li site, Li(2) is bonded in a T-shaped geometry to one O(1), one O(14), and one O(6) atom. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(2), one O(3), and one O(9) atom. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(5), one O(8), and two equivalent O(13) atoms. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(6), and two equivalent O(14) atoms. Bi(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(3), one O(4), and one O(5) atom to form distorted BiO7 pentagonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, and  an edgeedge with one P(1)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one Bi(1)O7 pentagonal bipyramid. In the second P site, P(2) is bonded to one O(1), one O(10), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. In the third P site, P(3) is bonded to one O(11), one O(13), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Li(3), one Bi(1), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Li(3), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(4), one Bi(1), and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(5), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLi3P trigonal pyramids. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(5), one Bi(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(5), one Bi(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded to one Li(3), two equivalent Li(4), and one P(3) atom to form distorted edge-sharing OLi3P trigonal pyramids. In the fourteenth O site, O(14) is bonded to one Li(2), two equivalent Li(5), and one P(4) atom to form a mixture of distorted corner and edge-sharing OLi3P trigonal pyramids.
Li5Bi(P2O7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(4), one O(6), one O(8), and one O(9) atom to form distorted LiO4 trigonal pyramids that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Li(1)-O(4) bond length is 2.19 Å. The Li(1)-O(6) bond length is 2.09 Å. The Li(1)-O(8) bond length is 2.04 Å. The Li(1)-O(9) bond length is 2.04 Å. In the second Li site, Li(2) is bonded in a T-shaped geometry to one O(1), one O(14), and one O(6) atom. The Li(2)-O(1) bond length is 2.02 Å. The Li(2)-O(14) bond length is 2.09 Å. The Li(2)-O(6) bond length is 2.01 Å. In the third Li site, Li(3) is bonded in a distorted rectangular see-saw-like geometry to one O(13), one O(2), one O(3), and one O(9) atom. The Li(3)-O(13) bond length is 2.11 Å. The Li(3)-O(2) bond length is 2.24 Å. The Li(3)-O(3) bond length is 2.08 Å. The Li(3)-O(9) bond length is 2.06 Å. In the fourth Li site, Li(4) is bonded in a 4-coordinate geometry to one O(5), one O(8), and two equivalent O(13) atoms. The Li(4)-O(5) bond length is 2.11 Å. The Li(4)-O(8) bond length is 2.02 Å. There is one shorter (2.06 Å) and one longer (2.19 Å) Li(4)-O(13) bond length. In the fifth Li site, Li(5) is bonded in a 5-coordinate geometry to one O(11), one O(12), one O(6), and two equivalent O(14) atoms. The Li(5)-O(11) bond length is 2.05 Å. The Li(5)-O(12) bond length is 2.27 Å. The Li(5)-O(6) bond length is 2.15 Å. There is one shorter (2.05 Å) and one longer (2.44 Å) Li(5)-O(14) bond length. Bi(1) is bonded to one O(1), one O(11), one O(12), one O(2), one O(3), one O(4), and one O(5) atom to form distorted BiO7 pentagonal bipyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  a cornercorner with one Li(1)O4 trigonal pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The Bi(1)-O(1) bond length is 2.50 Å. The Bi(1)-O(11) bond length is 2.36 Å. The Bi(1)-O(12) bond length is 2.25 Å. The Bi(1)-O(2) bond length is 2.64 Å. The Bi(1)-O(3) bond length is 2.65 Å. The Bi(1)-O(4) bond length is 2.52 Å. The Bi(1)-O(5) bond length is 2.32 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one Bi(1)O7 pentagonal bipyramid. The P(1)-O(2) bond length is 1.53 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(7) bond length is 1.61 Å. In the second P site, P(2) is bonded to one O(1), one O(10), one O(4), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Bi(1)O7 pentagonal bipyramids,  a cornercorner with one P(4)O4 tetrahedra, and corners with two equivalent Li(1)O4 trigonal pyramids. The P(2)-O(1) bond length is 1.54 Å. The P(2)-O(10) bond length is 1.62 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(6) bond length is 1.54 Å. In the third P site, P(3) is bonded to one O(11), one O(13), one O(7), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The P(3)-O(11) bond length is 1.55 Å. The P(3)-O(13) bond length is 1.53 Å. The P(3)-O(7) bond length is 1.65 Å. The P(3)-O(9) bond length is 1.52 Å. In the fourth P site, P(4) is bonded to one O(10), one O(12), one O(14), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Bi(1)O7 pentagonal bipyramid,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one Li(1)O4 trigonal pyramid. The P(4)-O(10) bond length is 1.63 Å. The P(4)-O(12) bond length is 1.55 Å. The P(4)-O(14) bond length is 1.53 Å. The P(4)-O(8) bond length is 1.51 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Bi(1), and one P(2) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Li(3), one Bi(1), and one P(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Li(3), one Bi(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Bi(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(4), one Bi(1), and one P(1) atom. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(5), and one P(2) atom to form a mixture of distorted corner and edge-sharing OLi3P trigonal pyramids. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(4), and one P(4) atom. In the ninth O site, O(9) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one P(3) atom. In the tenth O site, O(10) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(5), one Bi(1), and one P(3) atom. In the twelfth O site, O(12) is bonded in a 3-coordinate geometry to one Li(5), one Bi(1), and one P(4) atom. In the thirteenth O site, O(13) is bonded to one Li(3), two equivalent Li(4), and one P(3) atom to form distorted edge-sharing OLi3P trigonal pyramids. In the fourteenth O site, O(14) is bonded to one Li(2), two equivalent Li(5), and one P(4) atom to form a mixture of distorted corner and edge-sharing OLi3P trigonal pyramids.