Na5Bi(P2O7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(7) atoms. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(4), one O(5), one O(9), and two equivalent O(13) atoms. In the third Na site, Na(3) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(2), one O(6), one O(7), and one O(9) atom. In the fourth Na site, Na(4) is bonded to one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form NaO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(3), one O(4), one O(8), and one O(9) atom. Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(4), one O(5), one O(6), and one O(8) atom. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O5 square pyramid and  a cornercorner with one P(3)O4 tetrahedra. In the second P site, P(2) is bonded to one O(11), one O(13), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O5 square pyramid and  a cornercorner with one P(4)O4 tetrahedra. In the third P site, P(3) is bonded to one O(1), one O(12), one O(14), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O5 square pyramid and  a cornercorner with one P(1)O4 tetrahedra. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Na(4)O5 square pyramids and  a cornercorner with one P(2)O4 tetrahedra. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(1), one Na(5), one Bi(1), and one P(3) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(4), and one P(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one Na(5), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Bi(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Bi(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(4), one Bi(1), and one P(3) atom. In the seventh O site, O(7) is bonded to one Na(3), two equivalent Na(1), and one P(1) atom to form distorted edge-sharing ONa3P trigonal pyramids. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(4), one Na(5), one Bi(1), and one P(4) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Na(5), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(5), one Bi(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one Na(3), one Bi(1), and one P(3) atom. In the thirteenth O site, O(13) is bonded to one Na(5), two equivalent Na(2), and one P(2) atom to form distorted edge-sharing ONa3P trigonal pyramids. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom.
Na5Bi(P2O7)2 crystallizes in the triclinic P-1 space group. There are five inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(6), and two equivalent O(7) atoms. The Na(1)-O(1) bond length is 2.44 Å. The Na(1)-O(2) bond length is 2.59 Å. The Na(1)-O(3) bond length is 2.40 Å. The Na(1)-O(6) bond length is 2.94 Å. There is one shorter (2.39 Å) and one longer (2.58 Å) Na(1)-O(7) bond length. In the second Na site, Na(2) is bonded in a 5-coordinate geometry to one O(4), one O(5), one O(9), and two equivalent O(13) atoms. The Na(2)-O(4) bond length is 2.50 Å. The Na(2)-O(5) bond length is 2.39 Å. The Na(2)-O(9) bond length is 2.34 Å. There is one shorter (2.48 Å) and one longer (2.49 Å) Na(2)-O(13) bond length. In the third Na site, Na(3) is bonded in a distorted rectangular see-saw-like geometry to one O(12), one O(2), one O(6), one O(7), and one O(9) atom. The Na(3)-O(12) bond length is 2.38 Å. The Na(3)-O(2) bond length is 2.35 Å. The Na(3)-O(6) bond length is 2.42 Å. The Na(3)-O(7) bond length is 2.42 Å. The Na(3)-O(9) bond length is 2.91 Å. In the fourth Na site, Na(4) is bonded to one O(2), one O(3), one O(6), one O(8), and one O(9) atom to form NaO5 square pyramids that share  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The Na(4)-O(2) bond length is 2.30 Å. The Na(4)-O(3) bond length is 2.37 Å. The Na(4)-O(6) bond length is 2.51 Å. The Na(4)-O(8) bond length is 2.41 Å. The Na(4)-O(9) bond length is 2.35 Å. In the fifth Na site, Na(5) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(13), one O(3), one O(4), one O(8), and one O(9) atom. The Na(5)-O(1) bond length is 2.94 Å. The Na(5)-O(10) bond length is 2.40 Å. The Na(5)-O(13) bond length is 2.39 Å. The Na(5)-O(3) bond length is 2.62 Å. The Na(5)-O(4) bond length is 2.70 Å. The Na(5)-O(8) bond length is 2.90 Å. The Na(5)-O(9) bond length is 2.46 Å. Bi(1) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(12), one O(4), one O(5), one O(6), and one O(8) atom. The Bi(1)-O(1) bond length is 2.30 Å. The Bi(1)-O(10) bond length is 2.45 Å. The Bi(1)-O(12) bond length is 2.80 Å. The Bi(1)-O(4) bond length is 2.24 Å. The Bi(1)-O(5) bond length is 2.33 Å. The Bi(1)-O(6) bond length is 2.84 Å. The Bi(1)-O(8) bond length is 2.48 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(14), one O(2), one O(5), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O5 square pyramid and  a cornercorner with one P(3)O4 tetrahedra. The P(1)-O(14) bond length is 1.66 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(5) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.53 Å. In the second P site, P(2) is bonded to one O(11), one O(13), one O(3), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O5 square pyramid and  a cornercorner with one P(4)O4 tetrahedra. The P(2)-O(11) bond length is 1.64 Å. The P(2)-O(13) bond length is 1.52 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(1), one O(12), one O(14), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Na(4)O5 square pyramid and  a cornercorner with one P(1)O4 tetrahedra. The P(3)-O(1) bond length is 1.57 Å. The P(3)-O(12) bond length is 1.52 Å. The P(3)-O(14) bond length is 1.63 Å. The P(3)-O(6) bond length is 1.53 Å. In the fourth P site, P(4) is bonded to one O(10), one O(11), one O(8), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Na(4)O5 square pyramids and  a cornercorner with one P(2)O4 tetrahedra. The P(4)-O(10) bond length is 1.54 Å. The P(4)-O(11) bond length is 1.63 Å. The P(4)-O(8) bond length is 1.55 Å. The P(4)-O(9) bond length is 1.52 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a 1-coordinate geometry to one Na(1), one Na(5), one Bi(1), and one P(3) atom. In the second O site, O(2) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(4), and one P(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Na(1), one Na(4), one Na(5), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Bi(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(2), one Bi(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 1-coordinate geometry to one Na(1), one Na(3), one Na(4), one Bi(1), and one P(3) atom. In the seventh O site, O(7) is bonded to one Na(3), two equivalent Na(1), and one P(1) atom to form distorted edge-sharing ONa3P trigonal pyramids. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(4), one Na(5), one Bi(1), and one P(4) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Na(5), and one P(4) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(5), one Bi(1), and one P(4) atom. In the eleventh O site, O(11) is bonded in a bent 120 degrees geometry to one P(2) and one P(4) atom. In the twelfth O site, O(12) is bonded in a 2-coordinate geometry to one Na(3), one Bi(1), and one P(3) atom. In the thirteenth O site, O(13) is bonded to one Na(5), two equivalent Na(2), and one P(2) atom to form distorted edge-sharing ONa3P trigonal pyramids. In the fourteenth O site, O(14) is bonded in a bent 120 degrees geometry to one P(1) and one P(3) atom.