Na3TlCPO7 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms. Tl(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(7), and two equivalent O(5) atoms. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. P(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-54°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one C(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Tl(1), and one C(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Tl(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), one Tl(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to two equivalent Na(3), two equivalent Tl(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), one Tl(1), and one P(1) atom.
Na3TlCPO7 crystallizes in the monoclinic P2_1 space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra and edges with two equivalent Na(1)O6 octahedra. The Na(1)-O(3) bond length is 2.30 Å. The Na(1)-O(4) bond length is 2.30 Å. There is one shorter (2.40 Å) and one longer (2.49 Å) Na(1)-O(1) bond length. There is one shorter (2.42 Å) and one longer (2.60 Å) Na(1)-O(2) bond length. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(2), one O(3), one O(4), one O(6), and one O(7) atom. The Na(2)-O(1) bond length is 2.45 Å. The Na(2)-O(2) bond length is 2.65 Å. The Na(2)-O(3) bond length is 2.46 Å. The Na(2)-O(4) bond length is 2.91 Å. The Na(2)-O(6) bond length is 2.60 Å. The Na(2)-O(7) bond length is 2.98 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to two equivalent O(5), two equivalent O(6), and two equivalent O(7) atoms. There is one shorter (2.72 Å) and one longer (2.74 Å) Na(3)-O(5) bond length. There is one shorter (2.28 Å) and one longer (2.60 Å) Na(3)-O(6) bond length. There is one shorter (2.34 Å) and one longer (2.53 Å) Na(3)-O(7) bond length. Tl(1) is bonded in a 6-coordinate geometry to one O(2), one O(3), one O(4), one O(7), and two equivalent O(5) atoms. The Tl(1)-O(2) bond length is 2.66 Å. The Tl(1)-O(3) bond length is 2.57 Å. The Tl(1)-O(4) bond length is 2.43 Å. The Tl(1)-O(7) bond length is 2.58 Å. There is one shorter (2.66 Å) and one longer (2.78 Å) Tl(1)-O(5) bond length. C(1) is bonded in a trigonal planar geometry to one O(1), one O(2), and one O(5) atom. The C(1)-O(1) bond length is 1.30 Å. The C(1)-O(2) bond length is 1.30 Å. The C(1)-O(5) bond length is 1.31 Å. P(1) is bonded to one O(3), one O(4), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 35-54°. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.57 Å. The P(1)-O(6) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.55 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(1), and one C(1) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Tl(1), and one C(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Tl(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1), one Na(2), one Tl(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted single-bond geometry to two equivalent Na(3), two equivalent Tl(1), and one C(1) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), two equivalent Na(3), and one P(1) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Na(2), two equivalent Na(3), one Tl(1), and one P(1) atom.