Na6MgHf3Ge2(PO6)4 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(21), one O(23), one O(3), and one O(9) atom. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(12), one O(2), one O(22), one O(24), and one O(4) atom. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(14), one O(19), one O(2), one O(20), one O(21), and one O(22) atom. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(16), one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(23), one O(4), and one O(5) atom. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one O(10), one O(16), one O(21), one O(6), and one O(9) atom. Mg(1) is bonded to one O(12), one O(14), one O(17), one O(24), one O(4), and one O(6) atom to form MgO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one O(1), one O(15), one O(20), one O(21), one O(7), and one O(9) atom to form HfO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the second Hf site, Hf(2) is bonded to one O(10), one O(16), one O(19), one O(2), one O(22), and one O(8) atom to form HfO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. In the third Hf site, Hf(3) is bonded to one O(11), one O(13), one O(18), one O(23), one O(3), and one O(5) atom to form HfO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form GeO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. In the second Ge site, Ge(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form GeO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-44°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(21), one O(22), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-36°. In the second P site, P(2) is bonded to one O(23), one O(24), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-40°. In the third P site, P(3) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-40°. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-41°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one Hf(1), and one Ge(1) atom to form distorted corner-sharing ONa2HfGe trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(2), and one P(3) atom. In the third O site, O(3) is bonded to one Na(1), one Na(4), one Hf(3), and one Ge(2) atom to form ONa2HfGe trigonal pyramids that share  a cornercorner with one O(1)Na2HfGe trigonal pyramid and  a cornercorner with one O(12)Na2MgGe trigonal pyramid. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Mg(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(5), one Hf(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(6), one Mg(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to one Hf(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Hf(1), and one P(3) atom. In the tenth O site, O(10) is bonded to one Na(2), one Na(6), one Hf(2), and one Ge(1) atom to form distorted ONa2HfGe trigonal pyramids that share  a cornercorner with one O(1)Na2HfGe trigonal pyramid and  a cornercorner with one O(12)Na2MgGe trigonal pyramid. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(5), one Hf(3), and one P(4) atom. In the twelfth O site, O(12) is bonded to one Na(2), one Na(5), one Mg(1), and one Ge(2) atom to form corner-sharing ONa2MgGe trigonal pyramids. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Hf(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Mg(1), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Hf(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(4), one Na(6), one Hf(2), and one Ge(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Mg(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Na(4), one Hf(3), and one Ge(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Hf(2), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Hf(1), and one Ge(2) atom. In the twenty-first O site, O(21) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(6), one Hf(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Hf(2), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 5-coordinate geometry to one Na(1), one Na(4), one Na(5), one Hf(3), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Mg(1), and one P(2) atom.
Na6MgHf3Ge2(PO6)4 crystallizes in the triclinic P1 space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(1), one O(11), one O(21), one O(23), one O(3), and one O(9) atom. The Na(1)-O(1) bond length is 2.40 Å. The Na(1)-O(11) bond length is 2.53 Å. The Na(1)-O(21) bond length is 2.66 Å. The Na(1)-O(23) bond length is 2.58 Å. The Na(1)-O(3) bond length is 2.39 Å. The Na(1)-O(9) bond length is 2.59 Å. In the second Na site, Na(2) is bonded in a distorted hexagonal planar geometry to one O(10), one O(12), one O(2), one O(22), one O(24), and one O(4) atom. The Na(2)-O(10) bond length is 2.48 Å. The Na(2)-O(12) bond length is 2.28 Å. The Na(2)-O(2) bond length is 2.70 Å. The Na(2)-O(22) bond length is 2.75 Å. The Na(2)-O(24) bond length is 2.49 Å. The Na(2)-O(4) bond length is 2.53 Å. In the third Na site, Na(3) is bonded in a 7-coordinate geometry to one O(1), one O(14), one O(19), one O(2), one O(20), one O(21), and one O(22) atom. The Na(3)-O(1) bond length is 2.50 Å. The Na(3)-O(14) bond length is 2.78 Å. The Na(3)-O(19) bond length is 2.50 Å. The Na(3)-O(2) bond length is 2.40 Å. The Na(3)-O(20) bond length is 2.81 Å. The Na(3)-O(21) bond length is 2.78 Å. The Na(3)-O(22) bond length is 2.63 Å. In the fourth Na site, Na(4) is bonded in a 7-coordinate geometry to one O(16), one O(17), one O(18), one O(23), one O(24), one O(3), and one O(4) atom. The Na(4)-O(16) bond length is 3.00 Å. The Na(4)-O(17) bond length is 2.40 Å. The Na(4)-O(18) bond length is 2.76 Å. The Na(4)-O(23) bond length is 2.76 Å. The Na(4)-O(24) bond length is 2.39 Å. The Na(4)-O(3) bond length is 2.48 Å. The Na(4)-O(4) bond length is 2.38 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(11), one O(12), one O(14), one O(23), one O(4), and one O(5) atom. The Na(5)-O(11) bond length is 2.47 Å. The Na(5)-O(12) bond length is 2.36 Å. The Na(5)-O(14) bond length is 2.33 Å. The Na(5)-O(23) bond length is 2.47 Å. The Na(5)-O(4) bond length is 2.57 Å. The Na(5)-O(5) bond length is 2.92 Å. In the sixth Na site, Na(6) is bonded in a 5-coordinate geometry to one O(10), one O(16), one O(21), one O(6), and one O(9) atom. The Na(6)-O(10) bond length is 2.52 Å. The Na(6)-O(16) bond length is 2.41 Å. The Na(6)-O(21) bond length is 2.44 Å. The Na(6)-O(6) bond length is 2.58 Å. The Na(6)-O(9) bond length is 2.64 Å. Mg(1) is bonded to one O(12), one O(14), one O(17), one O(24), one O(4), and one O(6) atom to form MgO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The Mg(1)-O(12) bond length is 2.10 Å. The Mg(1)-O(14) bond length is 2.06 Å. The Mg(1)-O(17) bond length is 2.15 Å. The Mg(1)-O(24) bond length is 2.15 Å. The Mg(1)-O(4) bond length is 2.29 Å. The Mg(1)-O(6) bond length is 2.03 Å. There are three inequivalent Hf sites. In the first Hf site, Hf(1) is bonded to one O(1), one O(15), one O(20), one O(21), one O(7), and one O(9) atom to form HfO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The Hf(1)-O(1) bond length is 2.05 Å. The Hf(1)-O(15) bond length is 2.02 Å. The Hf(1)-O(20) bond length is 1.97 Å. The Hf(1)-O(21) bond length is 2.14 Å. The Hf(1)-O(7) bond length is 2.09 Å. The Hf(1)-O(9) bond length is 2.16 Å. In the second Hf site, Hf(2) is bonded to one O(10), one O(16), one O(19), one O(2), one O(22), and one O(8) atom to form HfO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The Hf(2)-O(10) bond length is 2.04 Å. The Hf(2)-O(16) bond length is 2.00 Å. The Hf(2)-O(19) bond length is 2.14 Å. The Hf(2)-O(2) bond length is 2.17 Å. The Hf(2)-O(22) bond length is 2.12 Å. The Hf(2)-O(8) bond length is 2.03 Å. In the third Hf site, Hf(3) is bonded to one O(11), one O(13), one O(18), one O(23), one O(3), and one O(5) atom to form HfO6 octahedra that share  a cornercorner with one Ge(1)O4 tetrahedra,  a cornercorner with one Ge(2)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The Hf(3)-O(11) bond length is 2.17 Å. The Hf(3)-O(13) bond length is 2.04 Å. The Hf(3)-O(18) bond length is 1.99 Å. The Hf(3)-O(23) bond length is 2.18 Å. The Hf(3)-O(3) bond length is 2.06 Å. The Hf(3)-O(5) bond length is 2.11 Å. There are two inequivalent Ge sites. In the first Ge site, Ge(1) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form GeO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-43°. The Ge(1)-O(1) bond length is 1.77 Å. The Ge(1)-O(10) bond length is 1.77 Å. The Ge(1)-O(14) bond length is 1.73 Å. The Ge(1)-O(18) bond length is 1.78 Å. In the second Ge site, Ge(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form GeO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-44°. The Ge(2)-O(12) bond length is 1.72 Å. The Ge(2)-O(16) bond length is 1.79 Å. The Ge(2)-O(20) bond length is 1.77 Å. The Ge(2)-O(3) bond length is 1.77 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(21), one O(22), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-36°. The P(1)-O(21) bond length is 1.58 Å. The P(1)-O(22) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(23), one O(24), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-40°. The P(2)-O(23) bond length is 1.57 Å. The P(2)-O(24) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(13), one O(17), one O(2), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-40°. The P(3)-O(13) bond length is 1.57 Å. The P(3)-O(17) bond length is 1.52 Å. The P(3)-O(2) bond length is 1.57 Å. The P(3)-O(9) bond length is 1.56 Å. In the fourth P site, P(4) is bonded to one O(11), one O(15), one O(19), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mg(1)O6 octahedra,  a cornercorner with one Hf(1)O6 octahedra,  a cornercorner with one Hf(2)O6 octahedra, and  a cornercorner with one Hf(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 14-41°. The P(4)-O(11) bond length is 1.56 Å. The P(4)-O(15) bond length is 1.55 Å. The P(4)-O(19) bond length is 1.56 Å. The P(4)-O(4) bond length is 1.53 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), one Na(3), one Hf(1), and one Ge(1) atom to form distorted corner-sharing ONa2HfGe trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(2), one Na(3), one Hf(2), and one P(3) atom. In the third O site, O(3) is bonded to one Na(1), one Na(4), one Hf(3), and one Ge(2) atom to form ONa2HfGe trigonal pyramids that share  a cornercorner with one O(1)Na2HfGe trigonal pyramid and  a cornercorner with one O(12)Na2MgGe trigonal pyramid. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(4), one Na(5), one Mg(1), and one P(4) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Na(5), one Hf(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Na(6), one Mg(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Hf(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to one Hf(2) and one P(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(1), one Na(6), one Hf(1), and one P(3) atom. In the tenth O site, O(10) is bonded to one Na(2), one Na(6), one Hf(2), and one Ge(1) atom to form distorted ONa2HfGe trigonal pyramids that share  a cornercorner with one O(1)Na2HfGe trigonal pyramid and  a cornercorner with one O(12)Na2MgGe trigonal pyramid. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(5), one Hf(3), and one P(4) atom. In the twelfth O site, O(12) is bonded to one Na(2), one Na(5), one Mg(1), and one Ge(2) atom to form corner-sharing ONa2MgGe trigonal pyramids. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Hf(3) and one P(3) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Mg(1), and one Ge(1) atom. In the fifteenth O site, O(15) is bonded in a linear geometry to one Hf(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(4), one Na(6), one Hf(2), and one Ge(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Mg(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Na(4), one Hf(3), and one Ge(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Hf(2), and one P(4) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Hf(1), and one Ge(2) atom. In the twenty-first O site, O(21) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(6), one Hf(1), and one P(1) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Hf(2), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 5-coordinate geometry to one Na(1), one Na(4), one Na(5), one Hf(3), and one P(2) atom. In the twenty-fourth O site, O(24) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(4), one Mg(1), and one P(2) atom.