NaBaNbBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted square co-planar geometry to four equivalent O(3) atoms. In the second Na site, Na(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Ba(2)O12 cuboctahedra, faces with four equivalent Nb(1)O6 octahedra, and faces with four equivalent Bi(1)O6 octahedra. In the second Ba site, Ba(2) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form distorted BaO12 cuboctahedra that share corners with four equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(1)O12 cuboctahedra, faces with four equivalent Nb(1)O6 octahedra, and faces with four equivalent Bi(1)O6 octahedra. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NbO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-12°. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-12°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), one Ba(1), one Ba(2), one Nb(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(2), one Nb(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one Ba(1), one Ba(2), one Nb(1), and one Bi(1) atom.
NaBaNbBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted square co-planar geometry to four equivalent O(3) atoms. All Na(1)-O(3) bond lengths are 2.80 Å. In the second Na site, Na(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(1) atoms. All Na(2)-O(1) bond lengths are 2.76 Å. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form BaO12 cuboctahedra that share corners with four equivalent Ba(2)O12 cuboctahedra, faces with two equivalent Ba(2)O12 cuboctahedra, faces with four equivalent Nb(1)O6 octahedra, and faces with four equivalent Bi(1)O6 octahedra. All Ba(1)-O(1) bond lengths are 3.00 Å. All Ba(1)-O(2) bond lengths are 2.96 Å. All Ba(1)-O(3) bond lengths are 2.93 Å. In the second Ba site, Ba(2) is bonded to four equivalent O(1), four equivalent O(2), and four equivalent O(3) atoms to form distorted BaO12 cuboctahedra that share corners with four equivalent Ba(1)O12 cuboctahedra, faces with two equivalent Ba(1)O12 cuboctahedra, faces with four equivalent Nb(1)O6 octahedra, and faces with four equivalent Bi(1)O6 octahedra. All Ba(2)-O(1) bond lengths are 2.99 Å. All Ba(2)-O(2) bond lengths are 2.77 Å. All Ba(2)-O(3) bond lengths are 3.17 Å. Nb(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NbO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-12°. Both Nb(1)-O(1) bond lengths are 2.01 Å. Both Nb(1)-O(2) bond lengths are 2.00 Å. Both Nb(1)-O(3) bond lengths are 2.01 Å. Bi(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form BiO6 octahedra that share corners with six equivalent Nb(1)O6 octahedra, faces with two equivalent Ba(1)O12 cuboctahedra, and faces with two equivalent Ba(2)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 10-12°. Both Bi(1)-O(1) bond lengths are 2.24 Å. Both Bi(1)-O(2) bond lengths are 2.23 Å. Both Bi(1)-O(3) bond lengths are 2.24 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(2), one Ba(1), one Ba(2), one Nb(1), and one Bi(1) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Ba(1), one Ba(2), one Nb(1), and one Bi(1) atom. In the third O site, O(3) is bonded in a 2-coordinate geometry to one Na(1), one Ba(1), one Ba(2), one Nb(1), and one Bi(1) atom.