Na6CaZr3Si2(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 8-coordinate geometry to one O(1), one O(13), 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 4-coordinate geometry to one O(17), 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. Ca(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 distorted CaO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Zr sites. In the first Zr site, Zr(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 ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Zr site, Zr(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 ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Zr site, Zr(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 ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-43°. In the second Si site, Si(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-46°. 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-37°. 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-46°. 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-45°. 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-44°. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Zr(1), and one Si(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Zr(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(4), one Zr(3), and one Si(2) atom. 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 Ca(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 Zr(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(6), one Ca(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to one Zr(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 Zr(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(6), one Zr(2), and one Si(1) atom. 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 Zr(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(5), one Ca(1), and one Si(2) atom. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Na(3), one Zr(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 Ca(1), and one Si(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(6), one Zr(2), and one Si(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Ca(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Zr(3) and one Si(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Zr(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 Zr(1), and one Si(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 Zr(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 Zr(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 Zr(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 Ca(1), and one P(2) atom.
Na6CaZr3Si2(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 2.54 Å. The Na(1)-O(11) bond length is 2.47 Å. The Na(1)-O(21) bond length is 2.69 Å. The Na(1)-O(23) bond length is 2.47 Å. The Na(1)-O(3) bond length is 2.47 Å. The Na(1)-O(9) bond length is 2.70 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 2.58 Å. The Na(2)-O(12) bond length is 2.39 Å. The Na(2)-O(2) bond length is 2.54 Å. The Na(2)-O(22) bond length is 2.61 Å. The Na(2)-O(24) bond length is 2.53 Å. The Na(2)-O(4) bond length is 2.55 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to one O(1), one O(13), 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 2.62 Å. The Na(3)-O(13) bond length is 2.99 Å. The Na(3)-O(14) bond length is 2.77 Å. The Na(3)-O(19) bond length is 2.53 Å. The Na(3)-O(2) bond length is 2.44 Å. The Na(3)-O(20) bond length is 2.97 Å. The Na(3)-O(21) bond length is 2.60 Å. The Na(3)-O(22) bond length is 2.66 Å. In the fourth Na site, Na(4) is bonded in a 4-coordinate geometry to one O(17), one O(23), one O(24), one O(3), and one O(4) atom. The Na(4)-O(17) bond length is 2.36 Å. The Na(4)-O(23) bond length is 2.87 Å. The Na(4)-O(24) bond length is 2.36 Å. The Na(4)-O(3) bond length is 2.47 Å. The Na(4)-O(4) bond length is 2.43 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 2.53 Å. The Na(5)-O(12) bond length is 2.37 Å. The Na(5)-O(14) bond length is 2.35 Å. The Na(5)-O(23) bond length is 2.42 Å. The Na(5)-O(4) bond length is 2.59 Å. The Na(5)-O(5) bond length is 2.88 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 2.53 Å. The Na(6)-O(16) bond length is 2.47 Å. The Na(6)-O(21) bond length is 2.63 Å. The Na(6)-O(6) bond length is 2.52 Å. The Na(6)-O(9) bond length is 2.55 Å. Ca(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 distorted CaO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Ca(1)-O(12) bond length is 2.32 Å. The Ca(1)-O(14) bond length is 2.26 Å. The Ca(1)-O(17) bond length is 2.32 Å. The Ca(1)-O(24) bond length is 2.35 Å. The Ca(1)-O(4) bond length is 2.43 Å. The Ca(1)-O(6) bond length is 2.21 Å. There are three inequivalent Zr sites. In the first Zr site, Zr(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 ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Zr(1)-O(1) bond length is 2.07 Å. The Zr(1)-O(15) bond length is 2.04 Å. The Zr(1)-O(20) bond length is 2.00 Å. The Zr(1)-O(21) bond length is 2.16 Å. The Zr(1)-O(7) bond length is 2.12 Å. The Zr(1)-O(9) bond length is 2.20 Å. In the second Zr site, Zr(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 ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Zr(2)-O(10) bond length is 2.07 Å. The Zr(2)-O(16) bond length is 2.05 Å. The Zr(2)-O(19) bond length is 2.17 Å. The Zr(2)-O(2) bond length is 2.22 Å. The Zr(2)-O(22) bond length is 2.17 Å. The Zr(2)-O(8) bond length is 2.06 Å. In the third Zr site, Zr(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 ZrO6 octahedra that share  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(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 Zr(3)-O(11) bond length is 2.23 Å. The Zr(3)-O(13) bond length is 2.07 Å. The Zr(3)-O(18) bond length is 2.03 Å. The Zr(3)-O(23) bond length is 2.24 Å. The Zr(3)-O(3) bond length is 2.10 Å. The Zr(3)-O(5) bond length is 2.16 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(10), one O(14), and one O(18) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-43°. The Si(1)-O(1) bond length is 1.65 Å. The Si(1)-O(10) bond length is 1.65 Å. The Si(1)-O(14) bond length is 1.61 Å. The Si(1)-O(18) bond length is 1.68 Å. In the second Si site, Si(2) is bonded to one O(12), one O(16), one O(20), and one O(3) atom to form SiO4 tetrahedra that share  a cornercorner with one Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 21-46°. The Si(2)-O(12) bond length is 1.61 Å. The Si(2)-O(16) bond length is 1.68 Å. The Si(2)-O(20) bond length is 1.65 Å. The Si(2)-O(3) bond length is 1.66 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-37°. The P(1)-O(21) bond length is 1.57 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 17-46°. 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 1.53 Å. The P(2)-O(8) bond length is 1.57 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 10-45°. The P(3)-O(13) bond length is 1.58 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 1.55 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 Ca(1)O6 octahedra,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Zr(2)O6 octahedra, and  a cornercorner with one Zr(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-44°. The P(4)-O(11) bond length is 1.55 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 1.54 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(3), one Zr(1), and one Si(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(3), one Zr(2), and one P(3) atom. In the third O site, O(3) is bonded in a distorted trigonal pyramidal geometry to one Na(1), one Na(4), one Zr(3), and one Si(2) atom. 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 Ca(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 Zr(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(6), one Ca(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted linear geometry to one Zr(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 Zr(1), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal pyramidal geometry to one Na(2), one Na(6), one Zr(2), and one Si(1) atom. 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 Zr(3), and one P(4) atom. In the twelfth O site, O(12) is bonded in a distorted rectangular see-saw-like geometry to one Na(2), one Na(5), one Ca(1), and one Si(2) atom. In the thirteenth O site, O(13) is bonded in a distorted linear geometry to one Na(3), one Zr(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 Ca(1), and one Si(1) atom. In the fifteenth O site, O(15) is bonded in a bent 150 degrees geometry to one Zr(1) and one P(4) atom. In the sixteenth O site, O(16) is bonded in a 3-coordinate geometry to one Na(6), one Zr(2), and one Si(2) atom. In the seventeenth O site, O(17) is bonded in a 3-coordinate geometry to one Na(4), one Ca(1), and one P(3) atom. In the eighteenth O site, O(18) is bonded in a distorted bent 150 degrees geometry to one Zr(3) and one Si(1) atom. In the nineteenth O site, O(19) is bonded in a 3-coordinate geometry to one Na(3), one Zr(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 Zr(1), and one Si(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 Zr(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 Zr(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 Zr(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 Ca(1), and one P(2) atom.