Na3CaSn(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), and one O(9) atom. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(11), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. Ca(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form CaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Sn(1) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form SnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-47°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-46°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ca(1), and one P(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Sn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Na(3), one Ca(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ca(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Sn(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), one Sn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(3), one Ca(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Ca(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(1), and one P(1) atom.
Na3CaSn(PO4)3 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to one O(1), one O(11), one O(12), one O(2), one O(5), and one O(6) atom. The Na(1)-O(1) bond length is 2.44 Å. The Na(1)-O(11) bond length is 2.79 Å. The Na(1)-O(12) bond length is 2.31 Å. The Na(1)-O(2) bond length is 2.58 Å. The Na(1)-O(5) bond length is 2.59 Å. The Na(1)-O(6) bond length is 2.44 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), one O(7), and one O(9) atom. The Na(2)-O(1) bond length is 2.47 Å. The Na(2)-O(10) bond length is 2.57 Å. The Na(2)-O(11) bond length is 2.38 Å. The Na(2)-O(12) bond length is 2.77 Å. The Na(2)-O(2) bond length is 2.44 Å. The Na(2)-O(7) bond length is 2.97 Å. The Na(2)-O(9) bond length is 2.49 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(11), one O(4), one O(5), one O(6), one O(7), and one O(8) atom. The Na(3)-O(11) bond length is 2.53 Å. The Na(3)-O(4) bond length is 2.79 Å. The Na(3)-O(5) bond length is 2.40 Å. The Na(3)-O(6) bond length is 2.59 Å. The Na(3)-O(7) bond length is 2.58 Å. The Na(3)-O(8) bond length is 2.70 Å. Ca(1) is bonded to one O(1), one O(11), one O(4), one O(5), one O(8), and one O(9) atom to form CaO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Ca(1)-O(1) bond length is 2.33 Å. The Ca(1)-O(11) bond length is 2.29 Å. The Ca(1)-O(4) bond length is 2.21 Å. The Ca(1)-O(5) bond length is 2.32 Å. The Ca(1)-O(8) bond length is 2.14 Å. The Ca(1)-O(9) bond length is 2.23 Å. Sn(1) is bonded to one O(10), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form SnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Sn(1)-O(10) bond length is 2.13 Å. The Sn(1)-O(12) bond length is 2.10 Å. The Sn(1)-O(2) bond length is 2.16 Å. The Sn(1)-O(3) bond length is 2.05 Å. The Sn(1)-O(6) bond length is 2.14 Å. The Sn(1)-O(7) bond length is 2.14 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(11), one O(12), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-46°. The P(1)-O(11) bond length is 1.54 Å. The P(1)-O(12) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(2), one O(5), one O(7), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-47°. The P(2)-O(2) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.61 Å. The P(2)-O(9) bond length is 1.51 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 19-46°. The P(3)-O(1) bond length is 1.53 Å. The P(3)-O(10) bond length is 1.60 Å. The P(3)-O(6) bond length is 1.59 Å. The P(3)-O(8) bond length is 1.50 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ca(1), and one P(3) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Sn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to one Na(3), one Ca(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), one Ca(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Sn(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Na(3), one Sn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(3), one Ca(1), and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one P(2) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Na(2), one Sn(1), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Ca(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(1), and one P(1) atom.