Na2CaTiP2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. Ca(1) is bonded to one O(1), one O(2), one O(3), one O(7), 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 S(1)O4 tetrahedra. Ti(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. In the second P site, P(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-40°. S(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-37°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ca(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1), one Ca(1), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ca(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Ti(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Ti(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ti(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ca(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ca(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ti(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Ti(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ti(1), and one P(2) atom.
Na2CaTiP2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to one O(10), one O(12), one O(2), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. The Na(1)-O(10) bond length is 2.38 Å. The Na(1)-O(12) bond length is 2.74 Å. The Na(1)-O(2) bond length is 3.01 Å. The Na(1)-O(3) bond length is 2.48 Å. The Na(1)-O(8) bond length is 2.30 Å. The Na(1)-O(9) bond length is 2.51 Å. There is one shorter (2.88 Å) and one longer (2.90 Å) Na(1)-O(4) bond length. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. The Na(2)-O(10) bond length is 2.71 Å. The Na(2)-O(11) bond length is 2.48 Å. The Na(2)-O(12) bond length is 2.54 Å. The Na(2)-O(7) bond length is 2.48 Å. The Na(2)-O(8) bond length is 2.84 Å. The Na(2)-O(9) bond length is 2.83 Å. Ca(1) is bonded to one O(1), one O(2), one O(3), one O(7), 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 S(1)O4 tetrahedra. The Ca(1)-O(1) bond length is 2.14 Å. The Ca(1)-O(2) bond length is 2.16 Å. The Ca(1)-O(3) bond length is 2.21 Å. The Ca(1)-O(7) bond length is 2.23 Å. The Ca(1)-O(8) bond length is 2.23 Å. The Ca(1)-O(9) bond length is 2.26 Å. Ti(1) is bonded to one O(10), one O(11), one O(12), one O(4), one O(5), and one O(6) atom to form TiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent S(1)O4 tetrahedra. The Ti(1)-O(10) bond length is 1.98 Å. The Ti(1)-O(11) bond length is 2.23 Å. The Ti(1)-O(12) bond length is 2.07 Å. The Ti(1)-O(4) bond length is 1.94 Å. The Ti(1)-O(5) bond length is 1.90 Å. The Ti(1)-O(6) bond length is 2.20 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(10), one O(4), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. The P(1)-O(1) bond length is 1.49 Å. The P(1)-O(10) bond length is 1.61 Å. The P(1)-O(4) bond length is 1.63 Å. The P(1)-O(7) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(12), one O(3), one O(5), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-40°. The P(2)-O(12) bond length is 1.59 Å. The P(2)-O(3) bond length is 1.50 Å. The P(2)-O(5) bond length is 1.64 Å. The P(2)-O(8) bond length is 1.53 Å. S(1) is bonded to one O(11), one O(2), one O(6), and one O(9) atom to form SO4 tetrahedra that share corners with two equivalent Ca(1)O6 octahedra and corners with two equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-37°. The S(1)-O(11) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.45 Å. The S(1)-O(6) bond length is 1.51 Å. The S(1)-O(9) bond length is 1.48 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ca(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Na(1), one Ca(1), and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Ca(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a distorted bent 150 degrees geometry to two equivalent Na(1), one Ti(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a linear geometry to one Ti(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Ti(1) and one S(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ca(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ca(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Ti(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Ti(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ti(1), and one P(2) atom.