Na3MgZr(PO4)3 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(2), one O(5), one O(6), one O(7), and two equivalent O(4) atoms. Mg(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 MgO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Zr(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 ZrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are three 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 Mg(1)O6 octahedra and corners with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. 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 Mg(1)O6 octahedra and corners with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra and corners with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-41°. 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 Mg(1), and one P(3) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Zr(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Zr(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 Mg(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Mg(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 Zr(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Zr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to one Mg(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Mg(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 Zr(1), and one P(3) 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 Mg(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zr(1), and one P(1) atom.
Na3MgZr(PO4)3 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 2.34 Å. The Na(1)-O(11) bond length is 2.61 Å. The Na(1)-O(12) bond length is 2.41 Å. The Na(1)-O(2) bond length is 2.76 Å. The Na(1)-O(5) bond length is 2.41 Å. The Na(1)-O(6) bond length is 2.57 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 2.40 Å. The Na(2)-O(10) bond length is 2.61 Å. The Na(2)-O(11) bond length is 2.41 Å. The Na(2)-O(12) bond length is 2.52 Å. The Na(2)-O(2) bond length is 2.55 Å. The Na(2)-O(9) bond length is 2.49 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(11), one O(2), one O(5), one O(6), one O(7), and two equivalent O(4) atoms. The Na(3)-O(11) bond length is 2.42 Å. The Na(3)-O(2) bond length is 2.65 Å. The Na(3)-O(5) bond length is 2.37 Å. The Na(3)-O(6) bond length is 2.56 Å. The Na(3)-O(7) bond length is 2.60 Å. There is one shorter (2.71 Å) and one longer (2.87 Å) Na(3)-O(4) bond length. Mg(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 MgO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Mg(1)-O(1) bond length is 2.17 Å. The Mg(1)-O(11) bond length is 2.14 Å. The Mg(1)-O(4) bond length is 2.09 Å. The Mg(1)-O(5) bond length is 2.17 Å. The Mg(1)-O(8) bond length is 2.00 Å. The Mg(1)-O(9) bond length is 2.10 Å. Zr(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 ZrO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. The Zr(1)-O(10) bond length is 2.10 Å. The Zr(1)-O(12) bond length is 2.14 Å. The Zr(1)-O(2) bond length is 2.19 Å. The Zr(1)-O(3) bond length is 2.02 Å. The Zr(1)-O(6) bond length is 2.14 Å. The Zr(1)-O(7) bond length is 2.09 Å. There are three 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 Mg(1)O6 octahedra and corners with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-45°. The P(1)-O(11) bond length is 1.54 Å. The P(1)-O(12) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.51 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 Mg(1)O6 octahedra and corners with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-41°. The P(2)-O(2) bond length is 1.58 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.58 Å. The P(2)-O(9) bond length is 1.52 Å. In the third P site, P(3) is bonded to one O(1), one O(10), one O(6), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mg(1)O6 octahedra and corners with two equivalent Zr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-41°. The P(3)-O(1) bond length is 1.53 Å. The P(3)-O(10) bond length is 1.58 Å. The P(3)-O(6) bond length is 1.58 Å. The P(3)-O(8) 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 Mg(1), and one P(3) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Zr(1), and one P(2) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Zr(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 Mg(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a rectangular see-saw-like geometry to one Na(1), one Na(3), one Mg(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 Zr(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Na(3), one Zr(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to one Mg(1) and one P(3) atom. In the ninth O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Mg(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 Zr(1), and one P(3) 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 Mg(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(2), one Zr(1), and one P(1) atom.