NaBaPrBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. In the second Na site, Na(2) is bonded in a square co-planar geometry to four equivalent O(3) 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 distorted BaO12 cuboctahedra that share faces with four equivalent Pr(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. In the second Ba site, Ba(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. Pr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form PrO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 22-31°. 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 Pr(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 22-31°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ba(2), one Pr(1), and one Bi(1) atom to form distorted OBa2PrBi trigonal pyramids that share corners with four equivalent O(2)BaNaPrBi tetrahedra, corners with six equivalent O(1)Ba2PrBi trigonal pyramids, edges with two equivalent O(2)BaNaPrBi tetrahedra, and  an edgeedge with one O(1)Ba2PrBi trigonal pyramid. In the second O site, O(2) is bonded to one Na(1), one Ba(1), one Pr(1), and one Bi(1) atom to form distorted OBaNaPrBi tetrahedra that share corners with six equivalent O(2)BaNaPrBi tetrahedra, corners with four equivalent O(1)Ba2PrBi trigonal pyramids,  an edgeedge with one O(2)BaNaPrBi tetrahedra, and edges with two equivalent O(1)Ba2PrBi trigonal pyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), one Ba(1), one Ba(2), one Pr(1), and one Bi(1) atom.
NaBaPrBiO6 crystallizes in the orthorhombic Pnnn space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to four equivalent O(2) atoms. All Na(1)-O(2) bond lengths are 2.56 Å. In the second Na site, Na(2) is bonded in a square co-planar geometry to four equivalent O(3) atoms. All Na(2)-O(3) bond lengths are 2.57 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 distorted BaO12 cuboctahedra that share faces with four equivalent Pr(1)O6 octahedra and faces with four equivalent Bi(1)O6 octahedra. All Ba(1)-O(1) bond lengths are 2.95 Å. All Ba(1)-O(2) bond lengths are 2.94 Å. All Ba(1)-O(3) bond lengths are 3.30 Å. In the second Ba site, Ba(2) is bonded in a body-centered cubic geometry to four equivalent O(1) and four equivalent O(3) atoms. All Ba(2)-O(1) bond lengths are 2.71 Å. All Ba(2)-O(3) bond lengths are 2.99 Å. Pr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form PrO6 octahedra that share corners with six equivalent Bi(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 22-31°. Both Pr(1)-O(1) bond lengths are 2.34 Å. Both Pr(1)-O(2) bond lengths are 2.39 Å. Both Pr(1)-O(3) bond lengths are 2.38 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 Pr(1)O6 octahedra and faces with two equivalent Ba(1)O12 cuboctahedra. The corner-sharing octahedral tilt angles range from 22-31°. Both Bi(1)-O(1) bond lengths are 2.14 Å. Both Bi(1)-O(2) bond lengths are 2.14 Å. Both Bi(1)-O(3) bond lengths are 2.15 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Ba(1), one Ba(2), one Pr(1), and one Bi(1) atom to form distorted OBa2PrBi trigonal pyramids that share corners with four equivalent O(2)BaNaPrBi tetrahedra, corners with six equivalent O(1)Ba2PrBi trigonal pyramids, edges with two equivalent O(2)BaNaPrBi tetrahedra, and  an edgeedge with one O(1)Ba2PrBi trigonal pyramid. In the second O site, O(2) is bonded to one Na(1), one Ba(1), one Pr(1), and one Bi(1) atom to form distorted OBaNaPrBi tetrahedra that share corners with six equivalent O(2)BaNaPrBi tetrahedra, corners with four equivalent O(1)Ba2PrBi trigonal pyramids,  an edgeedge with one O(2)BaNaPrBi tetrahedra, and edges with two equivalent O(1)Ba2PrBi trigonal pyramids. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(2), one Ba(1), one Ba(2), one Pr(1), and one Bi(1) atom.