Na3TaZnSi(PO6)2 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 6-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(9) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(5), one O(6), one O(7), one O(8), and two equivalent O(4) atoms. Ta(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 TaO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. Zn(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 distorted ZnO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. Si(1) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Ta(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-41°. There are two 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 Ta(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-45°. 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 Ta(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-44°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ta(1), and one P(2) atom. In the third O site, O(3) is bonded in a linear geometry to one Ta(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(3), one Zn(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 Zn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(3), one Ta(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Ta(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Zn(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Zn(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 Ta(1), and one Si(1) 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 Zn(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 Ta(1), and one P(1) atom.
Na3TaZnSi(PO6)2 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 2.27 Å. The Na(1)-O(11) bond length is 2.68 Å. The Na(1)-O(12) bond length is 2.43 Å. The Na(1)-O(2) bond length is 2.68 Å. The Na(1)-O(5) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.51 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(12), one O(2), and one O(9) atom. The Na(2)-O(1) bond length is 2.33 Å. The Na(2)-O(10) bond length is 2.56 Å. The Na(2)-O(11) bond length is 2.37 Å. The Na(2)-O(12) bond length is 2.75 Å. The Na(2)-O(2) bond length is 2.45 Å. The Na(2)-O(9) bond length is 2.40 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(5), one O(6), one O(7), one O(8), and two equivalent O(4) atoms. The Na(3)-O(11) bond length is 2.44 Å. The Na(3)-O(5) bond length is 2.37 Å. The Na(3)-O(6) bond length is 2.51 Å. The Na(3)-O(7) bond length is 2.62 Å. The Na(3)-O(8) bond length is 2.70 Å. There is one shorter (2.74 Å) and one longer (2.87 Å) Na(3)-O(4) bond length. Ta(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 TaO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Ta(1)-O(10) bond length is 1.96 Å. The Ta(1)-O(12) bond length is 2.04 Å. The Ta(1)-O(2) bond length is 2.10 Å. The Ta(1)-O(3) bond length is 1.95 Å. The Ta(1)-O(6) bond length is 2.00 Å. The Ta(1)-O(7) bond length is 2.02 Å. Zn(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 distorted ZnO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Zn(1)-O(1) bond length is 2.07 Å. The Zn(1)-O(11) bond length is 2.27 Å. The Zn(1)-O(4) bond length is 2.09 Å. The Zn(1)-O(5) bond length is 2.34 Å. The Zn(1)-O(8) bond length is 1.90 Å. The Zn(1)-O(9) bond length is 2.10 Å. Si(1) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Ta(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-41°. The Si(1)-O(1) bond length is 1.61 Å. The Si(1)-O(10) bond length is 1.72 Å. The Si(1)-O(6) bond length is 1.69 Å. The Si(1)-O(8) bond length is 1.58 Å. There are two 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 Ta(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-45°. The P(1)-O(11) bond length is 1.53 Å. The P(1)-O(12) bond length is 1.58 Å. The P(1)-O(3) bond length is 1.60 Å. The P(1)-O(4) bond length is 1.50 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 Ta(1)O6 octahedra and corners with two equivalent Zn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-44°. The P(2)-O(2) bond length is 1.60 Å. The P(2)-O(5) bond length is 1.51 Å. The P(2)-O(7) bond length is 1.61 Å. The P(2)-O(9) bond length is 1.51 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(2), one Zn(1), and one Si(1) atom. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Ta(1), and one P(2) atom. In the third O site, O(3) is bonded in a linear geometry to one Ta(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 2-coordinate geometry to two equivalent Na(3), one Zn(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 Zn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(3), one Ta(1), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Ta(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Zn(1), and one Si(1) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Zn(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 Ta(1), and one Si(1) 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 Zn(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 Ta(1), and one P(1) atom.