Na8Bi5O14 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and crystallizes in the triclinic P-1 space group. There are nine inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to one Bi(3), one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms. In the second Na site, Na(2) is bonded to two equivalent Bi(4), two equivalent O(10), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaBi2O6 hexagonal bipyramids that share corners with two equivalent O(13)Na2Bi3 trigonal bipyramids. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(1), one O(6), one O(7), and one O(9) atom. In the fourth Na site, Na(4) is bonded in a 2-coordinate geometry to one Bi(1), one O(1), one O(10), one O(11), one O(2), and one O(9) atom. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one Bi(2), one O(11), one O(2), one O(4), one O(6), and two equivalent O(5) atoms. In the sixth Na site, Na(6) is bonded in a 2-coordinate geometry to one O(11), one O(14), one O(3), and one O(5) atom. In the seventh Na site, Na(7) is bonded in a 3-coordinate geometry to one O(10), one O(13), one O(7), one O(9), and two equivalent O(14) atoms. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(4), one O(9), and two equivalent O(12) atoms. In the ninth Na site, Na(9) is bonded in a 2-coordinate geometry to two equivalent O(11), two equivalent O(13), and two equivalent O(9) atoms. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one Na(4), one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom. In the second Bi site, Bi(2) is bonded in a 1-coordinate geometry to one Na(5), one O(10), one O(14), one O(2), one O(4), one O(5), and one O(8) atom. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one Na(1), one O(12), one O(13), one O(3), one O(4), and one O(9) atom. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one Na(2), one O(10), one O(11), one O(12), one O(13), one O(6), and one O(8) atom. In the fifth Bi site, Bi(5) is bonded in a 4-coordinate geometry to one O(13), one O(14), one O(7), and one O(8) atom. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Na(4), and one Bi(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(4), one Na(5), one Bi(1), and one Bi(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(6), two equivalent Na(1), one Bi(1), and one Bi(3) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(5), one Na(8), one Bi(2), and one Bi(3) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(6), two equivalent Na(5), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(5), one Bi(1), and one Bi(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(3), one Na(7), one Bi(1), and one Bi(5) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(1), one Bi(2), one Bi(4), and one Bi(5) atom. In the ninth O site, O(9) is bonded in a 6-coordinate geometry to one Na(3), one Na(4), one Na(7), one Na(8), one Na(9), and one Bi(3) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(7), one Bi(2), and one Bi(4) atom. In the eleventh O site, O(11) is bonded in a 6-coordinate geometry to one Na(4), one Na(5), one Na(6), one Na(8), one Na(9), and one Bi(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Na(8), one Bi(3), and one Bi(4) atom. In the thirteenth O site, O(13) is bonded to one Na(7), one Na(9), one Bi(3), one Bi(4), and one Bi(5) atom to form distorted ONa2Bi3 trigonal bipyramids that share  a cornercorner with one Na(2)Bi2O6 hexagonal bipyramid and  a cornercorner with one O(13)Na2Bi3 trigonal bipyramid. In the fourteenth O site, O(14) is bonded in a 6-coordinate geometry to one Na(6), one Na(8), two equivalent Na(7), one Bi(2), and one Bi(5) atom.
Na8Bi5O14 is Pb (Zr_0.50 Ti_0.48) O_3-like structured and crystallizes in the triclinic P-1 space group. There are nine inequivalent Na sites. In the first Na site, Na(1) is bonded in a 2-coordinate geometry to one Bi(3), one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms. The Na(1)-Bi(3) bond length is 2.60 Å. The Na(1)-O(1) bond length is 2.86 Å. The Na(1)-O(2) bond length is 2.79 Å. The Na(1)-O(4) bond length is 2.74 Å. The Na(1)-O(5) bond length is 2.33 Å. There is one shorter (2.36 Å) and one longer (2.90 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to two equivalent Bi(4), two equivalent O(10), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaBi2O6 hexagonal bipyramids that share corners with two equivalent O(13)Na2Bi3 trigonal bipyramids. Both Na(2)-Bi(4) bond lengths are 2.60 Å. Both Na(2)-O(10) bond lengths are 2.55 Å. Both Na(2)-O(2) bond lengths are 2.75 Å. Both Na(2)-O(6) bond lengths are 2.25 Å. In the third Na site, Na(3) is bonded in a 4-coordinate geometry to one O(1), one O(6), one O(7), and one O(9) atom. The Na(3)-O(1) bond length is 2.55 Å. The Na(3)-O(6) bond length is 2.79 Å. The Na(3)-O(7) bond length is 2.52 Å. The Na(3)-O(9) bond length is 2.01 Å. In the fourth Na site, Na(4) is bonded in a 2-coordinate geometry to one Bi(1), one O(1), one O(10), one O(11), one O(2), and one O(9) atom. The Na(4)-Bi(1) bond length is 2.50 Å. The Na(4)-O(1) bond length is 2.03 Å. The Na(4)-O(10) bond length is 2.82 Å. The Na(4)-O(11) bond length is 2.29 Å. The Na(4)-O(2) bond length is 2.74 Å. The Na(4)-O(9) bond length is 2.84 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one Bi(2), one O(11), one O(2), one O(4), one O(6), and two equivalent O(5) atoms. The Na(5)-Bi(2) bond length is 2.49 Å. The Na(5)-O(11) bond length is 2.79 Å. The Na(5)-O(2) bond length is 2.54 Å. The Na(5)-O(4) bond length is 2.20 Å. The Na(5)-O(6) bond length is 2.81 Å. There is one shorter (2.50 Å) and one longer (2.77 Å) Na(5)-O(5) bond length. In the sixth Na site, Na(6) is bonded in a 2-coordinate geometry to one O(11), one O(14), one O(3), and one O(5) atom. The Na(6)-O(11) bond length is 2.86 Å. The Na(6)-O(14) bond length is 2.35 Å. The Na(6)-O(3) bond length is 2.51 Å. The Na(6)-O(5) bond length is 2.70 Å. In the seventh Na site, Na(7) is bonded in a 3-coordinate geometry to one O(10), one O(13), one O(7), one O(9), and two equivalent O(14) atoms. The Na(7)-O(10) bond length is 2.94 Å. The Na(7)-O(13) bond length is 2.52 Å. The Na(7)-O(7) bond length is 2.61 Å. The Na(7)-O(9) bond length is 2.70 Å. There is one shorter (2.93 Å) and one longer (2.96 Å) Na(7)-O(14) bond length. In the eighth Na site, Na(8) is bonded in a 6-coordinate geometry to one O(11), one O(14), one O(4), one O(9), and two equivalent O(12) atoms. The Na(8)-O(11) bond length is 2.20 Å. The Na(8)-O(14) bond length is 2.71 Å. The Na(8)-O(4) bond length is 2.82 Å. The Na(8)-O(9) bond length is 2.75 Å. There is one shorter (2.63 Å) and one longer (2.72 Å) Na(8)-O(12) bond length. In the ninth Na site, Na(9) is bonded in a 2-coordinate geometry to two equivalent O(11), two equivalent O(13), and two equivalent O(9) atoms. Both Na(9)-O(11) bond lengths are 2.87 Å. Both Na(9)-O(13) bond lengths are 2.89 Å. Both Na(9)-O(9) bond lengths are 2.43 Å. There are five inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a 7-coordinate geometry to one Na(4), one O(1), one O(2), one O(3), one O(6), one O(7), and one O(8) atom. The Bi(1)-O(1) bond length is 2.18 Å. The Bi(1)-O(2) bond length is 2.18 Å. The Bi(1)-O(3) bond length is 2.43 Å. The Bi(1)-O(6) bond length is 2.61 Å. The Bi(1)-O(7) bond length is 1.96 Å. The Bi(1)-O(8) bond length is 2.61 Å. In the second Bi site, Bi(2) is bonded in a 1-coordinate geometry to one Na(5), one O(10), one O(14), one O(2), one O(4), one O(5), and one O(8) atom. The Bi(2)-O(10) bond length is 2.58 Å. The Bi(2)-O(14) bond length is 2.50 Å. The Bi(2)-O(2) bond length is 2.72 Å. The Bi(2)-O(4) bond length is 2.63 Å. The Bi(2)-O(5) bond length is 1.92 Å. The Bi(2)-O(8) bond length is 2.56 Å. In the third Bi site, Bi(3) is bonded in a 6-coordinate geometry to one Na(1), one O(12), one O(13), one O(3), one O(4), and one O(9) atom. The Bi(3)-O(12) bond length is 2.64 Å. The Bi(3)-O(13) bond length is 2.26 Å. The Bi(3)-O(3) bond length is 2.52 Å. The Bi(3)-O(4) bond length is 2.23 Å. The Bi(3)-O(9) bond length is 2.39 Å. In the fourth Bi site, Bi(4) is bonded in a 7-coordinate geometry to one Na(2), one O(10), one O(11), one O(12), one O(13), one O(6), and one O(8) atom. The Bi(4)-O(10) bond length is 1.96 Å. The Bi(4)-O(11) bond length is 2.36 Å. The Bi(4)-O(12) bond length is 1.99 Å. The Bi(4)-O(13) bond length is 2.39 Å. The Bi(4)-O(6) bond length is 2.52 Å. The Bi(4)-O(8) bond length is 2.68 Å. In the fifth Bi site, Bi(5) is bonded in a 4-coordinate geometry to one O(13), one O(14), one O(7), and one O(8) atom. The Bi(5)-O(13) bond length is 2.60 Å. The Bi(5)-O(14) bond length is 2.00 Å. The Bi(5)-O(7) bond length is 2.26 Å. The Bi(5)-O(8) bond length is 2.38 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Na(4), and one Bi(1) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Na(1), one Na(2), one Na(4), one Na(5), one Bi(1), and one Bi(2) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(6), two equivalent Na(1), one Bi(1), and one Bi(3) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(1), one Na(5), one Na(8), one Bi(2), and one Bi(3) atom. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to one Na(1), one Na(6), two equivalent Na(5), and one Bi(2) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(5), one Bi(1), and one Bi(4) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(3), one Na(7), one Bi(1), and one Bi(5) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Bi(1), one Bi(2), one Bi(4), and one Bi(5) atom. In the ninth O site, O(9) is bonded in a 6-coordinate geometry to one Na(3), one Na(4), one Na(7), one Na(8), one Na(9), and one Bi(3) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(7), one Bi(2), and one Bi(4) atom. In the eleventh O site, O(11) is bonded in a 6-coordinate geometry to one Na(4), one Na(5), one Na(6), one Na(8), one Na(9), and one Bi(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to two equivalent Na(8), one Bi(3), and one Bi(4) atom. In the thirteenth O site, O(13) is bonded to one Na(7), one Na(9), one Bi(3), one Bi(4), and one Bi(5) atom to form distorted ONa2Bi3 trigonal bipyramids that share  a cornercorner with one Na(2)Bi2O6 hexagonal bipyramid and  a cornercorner with one O(13)Na2Bi3 trigonal bipyramid. In the fourteenth O site, O(14) is bonded in a 6-coordinate geometry to one Na(6), one Na(8), two equivalent Na(7), one Bi(2), and one Bi(5) atom.