Na7Zr4Si5PO24 crystallizes in the triclinic P1 space group. There are seven inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(14), one O(23), one O(6), one O(7), and one O(8) atom. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(12), one O(15), one O(2), one O(21), one O(3), one O(6), one O(7), and one O(9) atom. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(17), one O(5), and one O(6) atom. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(13), one O(14), one O(20), one O(3), one O(8), and one O(9) atom. In the sixth Na site, Na(6) is bonded in a 8-coordinate geometry to one O(10), one O(13), one O(16), one O(18), one O(19), one O(22), one O(23), and one O(4) atom. In the seventh Na site, Na(7) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(17), one O(18), one O(19), and one O(24) atom. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(10), one O(12), one O(14), one O(20), one O(3), and one O(7) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to one O(1), one O(2), one O(4), one O(6), one O(8), and one O(9) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. In the third Zr site, Zr(3) is bonded to one O(16), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. In the fourth Zr site, Zr(4) is bonded to one O(11), one O(13), one O(15), one O(18), one O(22), and one O(5) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. There are five inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-43°. In the second Si site, Si(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-42°. In the third Si site, Si(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-39°. In the fourth Si site, Si(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-42°. In the fifth Si site, Si(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-46°. P(1) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-41°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Zr(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(3), one Zr(2), and one Si(4) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Zr(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Na(6), one Zr(2), and one Si(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Zr(4), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zr(2), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Zr(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Zr(2), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Zr(2), and one Si(3) atom. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one Na(6), one Zr(1), and one Si(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(7), one Zr(4), and one Si(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Zr(1), and one Si(5) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(5), one Na(6), one Zr(4), and one Si(2) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(5), one Zr(1), and one Si(3) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Na(7), one Zr(4), and one Si(3) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Zr(3), and one Si(4) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Na(4), one Na(7), one Zr(3), and one Si(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Na(6), one Na(7), one Zr(4), and one Si(5) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to one Na(6), one Na(7), one Zr(3), and one P(1) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Na(5), one Zr(1), and one P(1) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Na(3), one Zr(3), and one Si(2) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(6), one Zr(4), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one Na(2), one Na(6), one Zr(3), and one Si(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Na(7), one Zr(3), and one Si(1) atom.
Na7Zr4Si5PO24 crystallizes in the triclinic P1 space group. There are seven inequivalent Na sites. In the first Na site, Na(1) is bonded in a distorted hexagonal planar geometry to one O(11), one O(14), one O(18), one O(22), one O(3), and one O(7) atom. The Na(1)-O(11) bond length is 2.63 Å. The Na(1)-O(14) bond length is 2.72 Å. The Na(1)-O(18) bond length is 2.56 Å. The Na(1)-O(22) bond length is 2.55 Å. The Na(1)-O(3) bond length is 2.45 Å. The Na(1)-O(7) bond length is 2.71 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(1), one O(14), one O(23), one O(6), one O(7), and one O(8) atom. The Na(2)-O(1) bond length is 2.43 Å. The Na(2)-O(14) bond length is 2.53 Å. The Na(2)-O(23) bond length is 2.80 Å. The Na(2)-O(6) bond length is 2.53 Å. The Na(2)-O(7) bond length is 2.50 Å. The Na(2)-O(8) bond length is 2.67 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(12), one O(15), one O(2), one O(21), one O(3), one O(6), one O(7), and one O(9) atom. The Na(3)-O(12) bond length is 2.48 Å. The Na(3)-O(15) bond length is 2.87 Å. The Na(3)-O(2) bond length is 2.49 Å. The Na(3)-O(21) bond length is 2.72 Å. The Na(3)-O(3) bond length is 2.69 Å. The Na(3)-O(6) bond length is 2.69 Å. The Na(3)-O(7) bond length is 2.62 Å. The Na(3)-O(9) bond length is 2.55 Å. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one O(12), one O(16), one O(17), one O(5), and one O(6) atom. The Na(4)-O(12) bond length is 2.67 Å. The Na(4)-O(16) bond length is 2.38 Å. The Na(4)-O(17) bond length is 2.35 Å. The Na(4)-O(5) bond length is 2.52 Å. The Na(4)-O(6) bond length is 2.44 Å. In the fifth Na site, Na(5) is bonded in a 6-coordinate geometry to one O(13), one O(14), one O(20), one O(3), one O(8), and one O(9) atom. The Na(5)-O(13) bond length is 2.68 Å. The Na(5)-O(14) bond length is 2.72 Å. The Na(5)-O(20) bond length is 2.41 Å. The Na(5)-O(3) bond length is 2.86 Å. The Na(5)-O(8) bond length is 2.42 Å. The Na(5)-O(9) bond length is 2.49 Å. In the sixth Na site, Na(6) is bonded in a 8-coordinate geometry to one O(10), one O(13), one O(16), one O(18), one O(19), one O(22), one O(23), and one O(4) atom. The Na(6)-O(10) bond length is 2.84 Å. The Na(6)-O(13) bond length is 2.43 Å. The Na(6)-O(16) bond length is 2.44 Å. The Na(6)-O(18) bond length is 2.59 Å. The Na(6)-O(19) bond length is 2.63 Å. The Na(6)-O(22) bond length is 2.62 Å. The Na(6)-O(23) bond length is 2.74 Å. The Na(6)-O(4) bond length is 2.90 Å. In the seventh Na site, Na(7) is bonded in a 6-coordinate geometry to one O(11), one O(15), one O(17), one O(18), one O(19), and one O(24) atom. The Na(7)-O(11) bond length is 2.53 Å. The Na(7)-O(15) bond length is 2.94 Å. The Na(7)-O(17) bond length is 2.53 Å. The Na(7)-O(18) bond length is 2.52 Å. The Na(7)-O(19) bond length is 2.50 Å. The Na(7)-O(24) bond length is 2.51 Å. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(10), one O(12), one O(14), one O(20), one O(3), and one O(7) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. The Zr(1)-O(10) bond length is 2.03 Å. The Zr(1)-O(12) bond length is 2.09 Å. The Zr(1)-O(14) bond length is 2.12 Å. The Zr(1)-O(20) bond length is 2.17 Å. The Zr(1)-O(3) bond length is 2.17 Å. The Zr(1)-O(7) bond length is 2.10 Å. In the second Zr site, Zr(2) is bonded to one O(1), one O(2), one O(4), one O(6), one O(8), and one O(9) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. The Zr(2)-O(1) bond length is 2.20 Å. The Zr(2)-O(2) bond length is 2.10 Å. The Zr(2)-O(4) bond length is 2.03 Å. The Zr(2)-O(6) bond length is 2.18 Å. The Zr(2)-O(8) bond length is 2.09 Å. The Zr(2)-O(9) bond length is 2.08 Å. In the third Zr site, Zr(3) is bonded to one O(16), one O(17), one O(19), one O(21), one O(23), and one O(24) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. The Zr(3)-O(16) bond length is 2.14 Å. The Zr(3)-O(17) bond length is 2.11 Å. The Zr(3)-O(19) bond length is 2.28 Å. The Zr(3)-O(21) bond length is 2.01 Å. The Zr(3)-O(23) bond length is 2.11 Å. The Zr(3)-O(24) bond length is 2.08 Å. In the fourth Zr site, Zr(4) is bonded to one O(11), one O(13), one O(15), one O(18), one O(22), and one O(5) atom to form ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra,  a cornercorner with one Si(4)O4 tetrahedra,  a cornercorner with one Si(5)O4 tetrahedra, and  a cornercorner with one P(1)O4 tetrahedra. The Zr(4)-O(11) bond length is 2.11 Å. The Zr(4)-O(13) bond length is 2.12 Å. The Zr(4)-O(15) bond length is 2.03 Å. The Zr(4)-O(18) bond length is 2.16 Å. The Zr(4)-O(22) bond length is 2.26 Å. The Zr(4)-O(5) bond length is 2.04 Å. There are five inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(24), one O(3), one O(5), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 20-43°. The Si(1)-O(24) bond length is 1.63 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(5) bond length is 1.65 Å. The Si(1)-O(6) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to one O(13), one O(21), one O(7), and one O(8) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-42°. The Si(2)-O(13) bond length is 1.64 Å. The Si(2)-O(21) bond length is 1.64 Å. The Si(2)-O(7) bond length is 1.64 Å. The Si(2)-O(8) bond length is 1.63 Å. In the third Si site, Si(3) is bonded to one O(14), one O(15), one O(23), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-39°. The Si(3)-O(14) bond length is 1.64 Å. The Si(3)-O(15) bond length is 1.65 Å. The Si(3)-O(23) bond length is 1.64 Å. The Si(3)-O(9) bond length is 1.64 Å. In the fourth Si site, Si(4) is bonded to one O(10), one O(11), one O(16), and one O(2) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-42°. The Si(4)-O(10) bond length is 1.65 Å. The Si(4)-O(11) bond length is 1.64 Å. The Si(4)-O(16) bond length is 1.64 Å. The Si(4)-O(2) bond length is 1.64 Å. In the fifth Si site, Si(5) is bonded to one O(12), one O(17), one O(18), and one O(4) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 15-46°. The Si(5)-O(12) bond length is 1.65 Å. The Si(5)-O(17) bond length is 1.64 Å. The Si(5)-O(18) bond length is 1.65 Å. The Si(5)-O(4) bond length is 1.63 Å. P(1) is bonded to one O(1), one O(19), one O(20), and one O(22) atom to form PO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra,  a cornercorner with one Zr(3)O6 octahedra, and  a cornercorner with one Zr(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 22-41°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(19) bond length is 1.56 Å. The P(1)-O(20) bond length is 1.56 Å. The P(1)-O(22) bond length is 1.55 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(2), one Zr(2), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(3), one Zr(2), and one Si(4) atom. In the third O site, O(3) is bonded in a 5-coordinate geometry to one Na(1), one Na(3), one Na(5), one Zr(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a distorted linear geometry to one Na(6), one Zr(2), and one Si(5) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Zr(4), and one Si(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zr(2), and one Si(1) atom. In the seventh O site, O(7) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(3), one Zr(1), and one Si(2) atom. In the eighth O site, O(8) is bonded in a 4-coordinate geometry to one Na(2), one Na(5), one Zr(2), and one Si(2) atom. In the ninth O site, O(9) is bonded in a 4-coordinate geometry to one Na(3), one Na(5), one Zr(2), and one Si(3) atom. In the tenth O site, O(10) is bonded in a 2-coordinate geometry to one Na(6), one Zr(1), and one Si(4) atom. In the eleventh O site, O(11) is bonded in a 4-coordinate geometry to one Na(1), one Na(7), one Zr(4), and one Si(4) atom. In the twelfth O site, O(12) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one Zr(1), and one Si(5) atom. In the thirteenth O site, O(13) is bonded in a 4-coordinate geometry to one Na(5), one Na(6), one Zr(4), and one Si(2) atom. In the fourteenth O site, O(14) is bonded in a 5-coordinate geometry to one Na(1), one Na(2), one Na(5), one Zr(1), and one Si(3) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Na(3), one Na(7), one Zr(4), and one Si(3) atom. In the sixteenth O site, O(16) is bonded in a 4-coordinate geometry to one Na(4), one Na(6), one Zr(3), and one Si(4) atom. In the seventeenth O site, O(17) is bonded in a 4-coordinate geometry to one Na(4), one Na(7), one Zr(3), and one Si(5) atom. In the eighteenth O site, O(18) is bonded in a distorted trigonal bipyramidal geometry to one Na(1), one Na(6), one Na(7), one Zr(4), and one Si(5) atom. In the nineteenth O site, O(19) is bonded in a 4-coordinate geometry to one Na(6), one Na(7), one Zr(3), and one P(1) atom. In the twentieth O site, O(20) is bonded in a distorted T-shaped geometry to one Na(5), one Zr(1), and one P(1) atom. In the twenty-first O site, O(21) is bonded in a 3-coordinate geometry to one Na(3), one Zr(3), and one Si(2) atom. In the twenty-second O site, O(22) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(6), one Zr(4), and one P(1) atom. In the twenty-third O site, O(23) is bonded in a 4-coordinate geometry to one Na(2), one Na(6), one Zr(3), and one Si(3) atom. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one Na(7), one Zr(3), and one Si(1) atom.