NaCo4BiO12 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(5) atoms. Co(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Co(1)O6 octahedra and edges with two equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-35°. Bi(1) is bonded to two equivalent O(2), two equivalent O(4), and four equivalent O(1) atoms to form distorted BiO8 hexagonal bipyramids that share edges with eight equivalent Co(1)O6 octahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Co(1) and one Bi(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Co(1) and one Bi(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent Co(1) and one Bi(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent Co(1) atoms.
NaCo4BiO12 crystallizes in the orthorhombic Amm2 space group. Na(1) is bonded in a 4-coordinate geometry to two equivalent O(3) and two equivalent O(5) atoms. Both Na(1)-O(3) bond lengths are 2.22 Å. Both Na(1)-O(5) bond lengths are 2.24 Å. Co(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form CoO6 octahedra that share corners with six equivalent Co(1)O6 octahedra and edges with two equivalent Bi(1)O8 hexagonal bipyramids. The corner-sharing octahedral tilt angles range from 22-35°. The Co(1)-O(2) bond length is 1.91 Å. The Co(1)-O(3) bond length is 1.81 Å. The Co(1)-O(4) bond length is 1.91 Å. The Co(1)-O(5) bond length is 1.83 Å. There is one shorter (1.93 Å) and one longer (2.03 Å) Co(1)-O(1) bond length. Bi(1) is bonded to two equivalent O(2), two equivalent O(4), and four equivalent O(1) atoms to form distorted BiO8 hexagonal bipyramids that share edges with eight equivalent Co(1)O6 octahedra. Both Bi(1)-O(2) bond lengths are 2.34 Å. Both Bi(1)-O(4) bond lengths are 2.35 Å. All Bi(1)-O(1) bond lengths are 2.21 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to two equivalent Co(1) and one Bi(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to two equivalent Co(1) and one Bi(1) atom. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to one Na(1) and two equivalent Co(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent Co(1) and one Bi(1) atom. In the fifth O site, O(5) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent Co(1) atoms.