Na3CaInP2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(5), one O(6), one O(7), and one O(9) atom. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. In the third Na site, Na(3) 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. In(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 distorted InO6 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 In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-43°. 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 In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. 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 In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-37°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), 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 Ca(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(2), one In(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), 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(2), one Na(3), one Ca(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Ca(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one In(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one In(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(2) atom.
Na3CaInP2SO12 crystallizes in the monoclinic Cc space group. There are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(1), one O(11), one O(12), one O(5), one O(6), one O(7), and one O(9) atom. The Na(1)-O(1) bond length is 2.66 Å. The Na(1)-O(11) bond length is 2.61 Å. The Na(1)-O(12) bond length is 2.49 Å. The Na(1)-O(5) bond length is 2.83 Å. The Na(1)-O(6) bond length is 2.79 Å. The Na(1)-O(7) bond length is 2.50 Å. The Na(1)-O(9) bond length is 2.56 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(10), one O(12), one O(3), one O(8), one O(9), and two equivalent O(4) atoms. The Na(2)-O(10) bond length is 2.48 Å. The Na(2)-O(12) bond length is 2.68 Å. The Na(2)-O(3) bond length is 2.51 Å. The Na(2)-O(8) bond length is 2.34 Å. The Na(2)-O(9) bond length is 2.70 Å. There is one shorter (2.87 Å) and one longer (2.90 Å) Na(2)-O(4) bond length. In the third Na site, Na(3) 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(3)-O(10) bond length is 2.63 Å. The Na(3)-O(11) bond length is 2.73 Å. The Na(3)-O(12) bond length is 2.51 Å. The Na(3)-O(7) bond length is 2.60 Å. The Na(3)-O(8) bond length is 2.56 Å. The Na(3)-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 2.25 Å. The Ca(1)-O(2) bond length is 2.20 Å. The Ca(1)-O(3) bond length is 2.24 Å. The Ca(1)-O(7) bond length is 2.29 Å. The Ca(1)-O(8) bond length is 2.29 Å. The Ca(1)-O(9) bond length is 2.34 Å. In(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 distorted InO6 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 In(1)-O(10) bond length is 2.17 Å. The In(1)-O(11) bond length is 2.32 Å. The In(1)-O(12) bond length is 2.21 Å. The In(1)-O(4) bond length is 2.14 Å. The In(1)-O(5) bond length is 2.11 Å. The In(1)-O(6) bond length is 2.34 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 In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-43°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(10) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.58 Å. The P(1)-O(7) bond length is 1.53 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 In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. The P(2)-O(12) bond length is 1.60 Å. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.54 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 In(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-37°. The S(1)-O(11) bond length is 1.50 Å. The S(1)-O(2) bond length is 1.46 Å. The S(1)-O(6) bond length is 1.49 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 3-coordinate geometry to one Na(1), 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 Ca(1) and one S(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(2), one Ca(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(2), one In(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(1), one In(1), and one S(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(3), 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(2), one Na(3), one Ca(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Ca(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(3), one In(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one In(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one In(1), and one P(2) atom.