Na5Ag(TeO14)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(13), two equivalent O(2), two equivalent O(7), and two equivalent O(8) atoms to form distorted edge-sharing NaO8 hexagonal bipyramids. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(4), one O(5), and three equivalent O(9) atoms. In the third Na site, Na(3) is bonded to one O(10), one O(11), one O(12), one O(13), one O(6), and one O(7) atom to form distorted NaO6 trigonal bipyramids that share  a cornercorner with one Te(1)O5 square pyramid and  an edgeedge with one Na(1)O8 hexagonal bipyramid. Ag(1) is bonded in a distorted square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. Te(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form distorted TeO5 square pyramids that share  a cornercorner with one Na(3)O6 trigonal bipyramid. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Te(1) and one O(4) atom. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(1) and one O(13) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Te(1) and one O(10) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Te(1), and one O(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Na(2), one Ag(1), and one Te(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(3), one Ag(1), one Te(1), and one O(11) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one O(12) atom. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(1) and one O(14) atom. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to three equivalent Na(2) atoms. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one O(3) atom. In the eleventh O site, O(11) is bonded in a trigonal non-coplanar geometry to one Na(2), one Na(3), and one O(6) atom. In the twelfth O site, O(12) is bonded in an L-shaped geometry to one Na(3) and one O(7) atom. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Na(1), one Na(3), and one O(2) atom. In the fourteenth O site, O(14) is bonded in a single-bond geometry to one O(8) atom.
Na5Ag(TeO14)2 crystallizes in the triclinic P-1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(13), two equivalent O(2), two equivalent O(7), and two equivalent O(8) atoms to form distorted edge-sharing NaO8 hexagonal bipyramids. Both Na(1)-O(13) bond lengths are 2.47 Å. Both Na(1)-O(2) bond lengths are 2.72 Å. Both Na(1)-O(7) bond lengths are 2.44 Å. Both Na(1)-O(8) bond lengths are 2.79 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(4), one O(5), and three equivalent O(9) atoms. The Na(2)-O(10) bond length is 2.89 Å. The Na(2)-O(11) bond length is 2.56 Å. The Na(2)-O(4) bond length is 2.68 Å. The Na(2)-O(5) bond length is 2.39 Å. There are a spread of Na(2)-O(9) bond distances ranging from 2.36-2.98 Å. In the third Na site, Na(3) is bonded to one O(10), one O(11), one O(12), one O(13), one O(6), and one O(7) atom to form distorted NaO6 trigonal bipyramids that share  a cornercorner with one Te(1)O5 square pyramid and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The Na(3)-O(10) bond length is 2.37 Å. The Na(3)-O(11) bond length is 2.36 Å. The Na(3)-O(12) bond length is 2.37 Å. The Na(3)-O(13) bond length is 2.42 Å. The Na(3)-O(6) bond length is 2.77 Å. The Na(3)-O(7) bond length is 2.46 Å. Ag(1) is bonded in a distorted square co-planar geometry to two equivalent O(5) and two equivalent O(6) atoms. Both Ag(1)-O(5) bond lengths are 2.18 Å. Both Ag(1)-O(6) bond lengths are 2.50 Å. Te(1) is bonded to one O(1), one O(3), one O(4), one O(5), and one O(6) atom to form distorted TeO5 square pyramids that share  a cornercorner with one Na(3)O6 trigonal bipyramid. The Te(1)-O(1) bond length is 2.09 Å. The Te(1)-O(3) bond length is 2.61 Å. The Te(1)-O(4) bond length is 2.11 Å. The Te(1)-O(5) bond length is 1.88 Å. The Te(1)-O(6) bond length is 2.32 Å. There are fourteen inequivalent O sites. In the first O site, O(1) is bonded in a bent 120 degrees geometry to one Te(1) and one O(4) atom. The O(1)-O(4) bond length is 1.45 Å. In the second O site, O(2) is bonded in a 2-coordinate geometry to one Na(1) and one O(13) atom. The O(2)-O(13) bond length is 1.29 Å. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one Te(1) and one O(10) atom. The O(3)-O(10) bond length is 1.28 Å. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one Na(2), one Te(1), and one O(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Na(2), one Ag(1), and one Te(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(3), one Ag(1), one Te(1), and one O(11) atom. The O(6)-O(11) bond length is 1.34 Å. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(1), one Na(3), and one O(12) atom. The O(7)-O(12) bond length is 1.30 Å. In the eighth O site, O(8) is bonded in a bent 120 degrees geometry to one Na(1) and one O(14) atom. The O(8)-O(14) bond length is 1.24 Å. In the ninth O site, O(9) is bonded in a distorted bent 120 degrees geometry to three equivalent Na(2) atoms. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), and one O(3) atom. In the eleventh O site, O(11) is bonded in a trigonal non-coplanar geometry to one Na(2), one Na(3), and one O(6) atom. In the twelfth O site, O(12) is bonded in an L-shaped geometry to one Na(3) and one O(7) atom. In the thirteenth O site, O(13) is bonded in a distorted T-shaped geometry to one Na(1), one Na(3), and one O(2) atom. In the fourteenth O site, O(14) is bonded in a single-bond geometry to one O(8) atom.