Na2ZnSnP2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) 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 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. Zn(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 ZnO6 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. Sn(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 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 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 Zn(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. 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 Zn(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-41°. 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 Zn(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-38°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Zn(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 Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Sn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Sn(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Sn(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 Zn(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 Zn(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(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 Sn(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(2), one Sn(1), and one P(2) atom.
Na2ZnSnP2SO12 crystallizes in the monoclinic Cc space group. There are two inequivalent Na sites. In the first Na site, Na(1) 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(1)-O(10) bond length is 2.44 Å. The Na(1)-O(12) bond length is 2.52 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(8) bond length is 2.30 Å. The Na(1)-O(9) bond length is 2.44 Å. There is one shorter (2.76 Å) and one longer (2.79 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 2.74 Å. The Na(2)-O(11) bond length is 2.63 Å. The Na(2)-O(12) bond length is 2.55 Å. The Na(2)-O(7) bond length is 2.34 Å. The Na(2)-O(8) bond length is 2.48 Å. The Na(2)-O(9) bond length is 2.61 Å. Zn(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 ZnO6 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 Zn(1)-O(1) bond length is 1.99 Å. The Zn(1)-O(2) bond length is 2.05 Å. The Zn(1)-O(3) bond length is 2.04 Å. The Zn(1)-O(7) bond length is 2.05 Å. The Zn(1)-O(8) bond length is 2.19 Å. The Zn(1)-O(9) bond length is 2.21 Å. Sn(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 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 S(1)O4 tetrahedra. The Sn(1)-O(10) bond length is 2.06 Å. The Sn(1)-O(11) bond length is 2.15 Å. The Sn(1)-O(12) bond length is 2.09 Å. The Sn(1)-O(4) bond length is 2.05 Å. The Sn(1)-O(5) bond length is 2.02 Å. The Sn(1)-O(6) bond length is 2.14 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 Zn(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(10) bond length is 1.59 Å. The P(1)-O(4) bond length is 1.60 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 Zn(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-41°. The P(2)-O(12) bond length is 1.60 Å. The P(2)-O(3) bond length is 1.52 Å. The P(2)-O(5) bond length is 1.57 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 Zn(1)O6 octahedra and corners with two equivalent Sn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-38°. 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 1.51 Å. The S(1)-O(9) bond length is 1.47 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Zn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted bent 150 degrees geometry to one Zn(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 Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Sn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Sn(1) and one P(2) atom. In the sixth O site, O(6) is bonded in a bent 150 degrees geometry to one Sn(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 Zn(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 Zn(1), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Sn(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 Sn(1), and one S(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(2), one Sn(1), and one P(2) atom.