Li2NiBiO4 is alpha Po-derived structured and crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. In the second Li site, Li(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Bi(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Bi(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second Bi site, Bi(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Ni(1), one Bi(1), and one Bi(2) atom to form OLi3NiBi2 octahedra that share corners with six equivalent O(1)Li3NiBi2 octahedra, edges with four equivalent O(2)Li3Ni2Bi octahedra, edges with four equivalent O(3)Li3Ni2Bi octahedra, and edges with four equivalent O(1)Li3NiBi2 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Ni(1), and one Bi(1) atom to form OLi3Ni2Bi octahedra that share corners with two equivalent O(2)Li3Ni2Bi octahedra, corners with four equivalent O(3)Li3Ni2Bi octahedra, edges with two equivalent O(2)Li3Ni2Bi octahedra, edges with two equivalent O(3)Li3Ni2Bi octahedra, and edges with eight equivalent O(1)Li3NiBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Ni(1), and one Bi(2) atom to form OLi3Ni2Bi octahedra that share corners with two equivalent O(3)Li3Ni2Bi octahedra, corners with four equivalent O(2)Li3Ni2Bi octahedra, edges with two equivalent O(2)Li3Ni2Bi octahedra, edges with two equivalent O(3)Li3Ni2Bi octahedra, and edges with eight equivalent O(1)Li3NiBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.
Li2NiBiO4 is alpha Po-derived structured and crystallizes in the orthorhombic C222 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Li(1)-O(1) bond lengths are 2.38 Å. Both Li(1)-O(2) bond lengths are 2.23 Å. Both Li(1)-O(3) bond lengths are 2.20 Å. In the second Li site, Li(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Bi(2)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Li(2)-O(3) bond lengths are 2.20 Å. All Li(2)-O(1) bond lengths are 2.24 Å. In the third Li site, Li(3) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form LiO6 octahedra that share corners with two equivalent Bi(1)O6 octahedra, corners with four equivalent Li(2)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-8°. Both Li(3)-O(2) bond lengths are 2.29 Å. All Li(3)-O(1) bond lengths are 2.21 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent Bi(1)O6 octahedra, edges with two equivalent Bi(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-3°. Both Ni(1)-O(1) bond lengths are 2.10 Å. Both Ni(1)-O(2) bond lengths are 2.23 Å. Both Ni(1)-O(3) bond lengths are 2.21 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Bi(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Bi(1)-O(2) bond lengths are 2.18 Å. All Bi(1)-O(1) bond lengths are 2.19 Å. In the second Bi site, Bi(2) is bonded to two equivalent O(3) and four equivalent O(1) atoms to form BiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Bi(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Bi(2)-O(3) bond lengths are 2.27 Å. All Bi(2)-O(1) bond lengths are 2.26 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one Li(3), one Ni(1), one Bi(1), and one Bi(2) atom to form OLi3NiBi2 octahedra that share corners with six equivalent O(1)Li3NiBi2 octahedra, edges with four equivalent O(2)Li3Ni2Bi octahedra, edges with four equivalent O(3)Li3Ni2Bi octahedra, and edges with four equivalent O(1)Li3NiBi2 octahedra. The corner-sharing octahedral tilt angles range from 3-7°. In the second O site, O(2) is bonded to one Li(3), two equivalent Li(1), two equivalent Ni(1), and one Bi(1) atom to form OLi3Ni2Bi octahedra that share corners with two equivalent O(2)Li3Ni2Bi octahedra, corners with four equivalent O(3)Li3Ni2Bi octahedra, edges with two equivalent O(2)Li3Ni2Bi octahedra, edges with two equivalent O(3)Li3Ni2Bi octahedra, and edges with eight equivalent O(1)Li3NiBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°. In the third O site, O(3) is bonded to one Li(2), two equivalent Li(1), two equivalent Ni(1), and one Bi(2) atom to form OLi3Ni2Bi octahedra that share corners with two equivalent O(3)Li3Ni2Bi octahedra, corners with four equivalent O(2)Li3Ni2Bi octahedra, edges with two equivalent O(2)Li3Ni2Bi octahedra, edges with two equivalent O(3)Li3Ni2Bi octahedra, and edges with eight equivalent O(1)Li3NiBi2 octahedra. The corner-sharing octahedral tilt angles range from 0-1°.