Na4Zn2P2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), one O(7), and one O(8) atom. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(5), one O(6), one O(7), one O(9), and two equivalent O(1) atoms. In the third Na site, Na(3) 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 fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. There are two inequivalent Zn sites. In the first Zn site, 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 distorted 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. In the second Zn site, Zn(2) 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 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. 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 Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-42°. 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 Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-38°. 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 Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Zn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(3), one Zn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Zn(2), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Na(4), one Zn(1), and one P(1) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids. In the eighth O site, O(8) is bonded to one Na(1), one Na(3), one Na(4), one Zn(1), and one P(2) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded to one Na(1), one Na(3), one Na(4), one Zn(2), and one P(1) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(4), one Zn(2), and one S(1) atom. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Na(4), one Zn(2), and one P(2) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids.
Na4Zn2P2SO12 crystallizes in the monoclinic Cc space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 7-coordinate geometry to one O(10), one O(11), one O(2), one O(3), one O(5), one O(7), and one O(8) atom. The Na(1)-O(10) bond length is 2.46 Å. The Na(1)-O(11) bond length is 2.59 Å. The Na(1)-O(2) bond length is 2.72 Å. The Na(1)-O(3) bond length is 2.90 Å. The Na(1)-O(5) bond length is 2.54 Å. The Na(1)-O(7) bond length is 2.47 Å. The Na(1)-O(8) bond length is 2.49 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to one O(11), one O(12), one O(5), one O(6), one O(7), one O(9), and two equivalent O(1) atoms. The Na(2)-O(11) bond length is 2.57 Å. The Na(2)-O(12) bond length is 2.48 Å. The Na(2)-O(5) bond length is 2.91 Å. The Na(2)-O(6) bond length is 2.74 Å. The Na(2)-O(7) bond length is 2.50 Å. The Na(2)-O(9) bond length is 2.58 Å. There is one shorter (2.57 Å) and one longer (2.90 Å) Na(2)-O(1) bond length. In the third Na site, Na(3) 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(3)-O(10) bond length is 2.53 Å. The Na(3)-O(12) bond length is 2.49 Å. The Na(3)-O(3) bond length is 2.61 Å. The Na(3)-O(8) bond length is 2.46 Å. The Na(3)-O(9) bond length is 2.59 Å. There is one shorter (2.63 Å) and one longer (2.89 Å) Na(3)-O(4) bond length. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(10), one O(11), one O(12), one O(7), one O(8), and one O(9) atom. The Na(4)-O(10) bond length is 2.54 Å. The Na(4)-O(11) bond length is 2.66 Å. The Na(4)-O(12) bond length is 2.47 Å. The Na(4)-O(7) bond length is 2.54 Å. The Na(4)-O(8) bond length is 2.49 Å. The Na(4)-O(9) bond length is 2.63 Å. There are two inequivalent Zn sites. In the first Zn site, 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 distorted 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 2.05 Å. The Zn(1)-O(2) bond length is 2.09 Å. The Zn(1)-O(3) bond length is 2.01 Å. The Zn(1)-O(7) bond length is 2.18 Å. The Zn(1)-O(8) bond length is 2.22 Å. The Zn(1)-O(9) bond length is 2.26 Å. In the second Zn site, Zn(2) 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 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(2)-O(10) bond length is 2.09 Å. The Zn(2)-O(11) bond length is 2.36 Å. The Zn(2)-O(12) bond length is 2.22 Å. The Zn(2)-O(4) bond length is 1.97 Å. The Zn(2)-O(5) bond length is 2.02 Å. The Zn(2)-O(6) bond length is 2.19 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 Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 34-42°. The P(1)-O(1) bond length is 1.55 Å. The P(1)-O(10) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.57 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 Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 32-38°. The P(2)-O(12) bond length is 1.57 Å. The P(2)-O(3) bond length is 1.55 Å. The P(2)-O(5) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.57 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 Zn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 33-37°. The S(1)-O(11) bond length is 1.49 Å. The S(1)-O(2) bond length is 1.49 Å. The S(1)-O(6) bond length is 1.49 Å. The S(1)-O(9) bond length is 1.50 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Na(2), one Zn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zn(1), and one S(1) atom. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Zn(1), and one P(2) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(3), one Zn(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zn(2), and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(2), one Zn(2), and one S(1) atom. In the seventh O site, O(7) is bonded to one Na(1), one Na(2), one Na(4), one Zn(1), and one P(1) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids. In the eighth O site, O(8) is bonded to one Na(1), one Na(3), one Na(4), one Zn(1), and one P(2) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids. In the ninth O site, O(9) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zn(1), and one S(1) atom. In the tenth O site, O(10) is bonded to one Na(1), one Na(3), one Na(4), one Zn(2), and one P(1) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids. In the eleventh O site, O(11) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(4), one Zn(2), and one S(1) atom. In the twelfth O site, O(12) is bonded to one Na(2), one Na(3), one Na(4), one Zn(2), and one P(2) atom to form a mixture of distorted face, corner, and edge-sharing ONa3ZnP trigonal bipyramids.