Na(BiO2)2 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), two equivalent O(4), and three equivalent O(2) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. In the second Bi site, Bi(2) is bonded to one O(4), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Bi(1), and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded to two equivalent Na(1) and three equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing ONa2Bi3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(1) and three equivalent Bi(2) atoms to form a mixture of edge and corner-sharing ONa2Bi3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Bi(2), and two equivalent Bi(1) atoms.
Na(BiO2)2 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded in a 7-coordinate geometry to one O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms. The Na(1)-O(1) bond length is 2.82 Å. Both Na(1)-O(2) bond lengths are 2.69 Å. Both Na(1)-O(3) bond lengths are 2.69 Å. Both Na(1)-O(4) bond lengths are 2.87 Å. There are two inequivalent Bi sites. In the first Bi site, Bi(1) is bonded to one O(1), two equivalent O(4), and three equivalent O(2) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Bi(1)-O(1) bond length is 2.29 Å. Both Bi(1)-O(4) bond lengths are 2.42 Å. There are two shorter (2.37 Å) and one longer (2.38 Å) Bi(1)-O(2) bond length. In the second Bi site, Bi(2) is bonded to one O(4), two equivalent O(1), and three equivalent O(3) atoms to form a mixture of edge and corner-sharing BiO6 octahedra. The corner-sharing octahedral tilt angles range from 50-60°. The Bi(2)-O(4) bond length is 2.26 Å. Both Bi(2)-O(1) bond lengths are 2.29 Å. There is one shorter (2.33 Å) and two longer (2.37 Å) Bi(2)-O(3) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Bi(1), and two equivalent Bi(2) atoms. In the second O site, O(2) is bonded to two equivalent Na(1) and three equivalent Bi(1) atoms to form a mixture of distorted edge and corner-sharing ONa2Bi3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Na(1) and three equivalent Bi(2) atoms to form a mixture of edge and corner-sharing ONa2Bi3 square pyramids. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Bi(2), and two equivalent Bi(1) atoms.