Na5PrO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Pr(1)O6 octahedra, and edges with four equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Pr(1)O6 octahedra, and edges with four equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pr(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pr(1)O6 octahedra, and edges with six equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. In the fourth Na site, Na(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pr(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pr(1)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. 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 two equivalent Na(3)O6 octahedra, corners with four equivalent Na(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Pr(1) atom to form a mixture of corner and edge-sharing ONa5Pr octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Pr(1) atom to form a mixture of corner and edge-sharing ONa5Pr octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Pr(1) atom to form a mixture of corner and edge-sharing ONa5Pr octahedra. The corner-sharing octahedral tilt angles range from 0-8°.
Na5PrO6 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with three equivalent Pr(1)O6 octahedra, and edges with four equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Na(1)-O(1) bond lengths are 2.46 Å. Both Na(1)-O(2) bond lengths are 2.45 Å. Both Na(1)-O(3) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(3)O6 octahedra, corners with four equivalent Na(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Pr(1)O6 octahedra, and edges with four equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-8°. Both Na(2)-O(1) bond lengths are 2.48 Å. Both Na(2)-O(2) bond lengths are 2.47 Å. Both Na(2)-O(3) bond lengths are 2.46 Å. In the third Na site, Na(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pr(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pr(1)O6 octahedra, and edges with six equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-6°. Both Na(3)-O(1) bond lengths are 2.59 Å. Both Na(3)-O(2) bond lengths are 2.42 Å. Both Na(3)-O(3) bond lengths are 2.44 Å. In the fourth Na site, Na(4) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Pr(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with two equivalent Na(2)O6 octahedra, edges with two equivalent Pr(1)O6 octahedra, edges with three equivalent Na(3)O6 octahedra, and edges with three equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-8°. There is one shorter (2.49 Å) and one longer (2.50 Å) Na(4)-O(1) bond length. There is one shorter (2.43 Å) and one longer (2.55 Å) Na(4)-O(2) bond length. There is one shorter (2.45 Å) and one longer (2.48 Å) Na(4)-O(3) bond length. 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 two equivalent Na(3)O6 octahedra, corners with four equivalent Na(4)O6 octahedra, edges with two equivalent Na(3)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, and edges with four equivalent Na(4)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. Both Pr(1)-O(1) bond lengths are 2.31 Å. Both Pr(1)-O(2) bond lengths are 2.32 Å. Both Pr(1)-O(3) bond lengths are 2.32 Å. There are three inequivalent O sites. In the first O site, O(3) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Pr(1) atom to form a mixture of corner and edge-sharing ONa5Pr octahedra. The corner-sharing octahedral tilt angles range from 0-8°. In the second O site, O(1) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Pr(1) atom to form a mixture of corner and edge-sharing ONa5Pr octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the third O site, O(2) is bonded to one Na(1), one Na(2), one Na(3), two equivalent Na(4), and one Pr(1) atom to form a mixture of corner and edge-sharing ONa5Pr octahedra. The corner-sharing octahedral tilt angles range from 0-8°.