Na3Zr2Si2PO12 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent O(12), two equivalent O(3), two equivalent O(7), and two equivalent O(9) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(10), two equivalent O(11), two equivalent O(4), and two equivalent O(8) atoms. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(12), one O(4), and two equivalent O(6) atoms. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and one O(9) atom. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(12), one O(2), one O(3), one O(5), 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, corners with two equivalent Si(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. In the second Zr site, Zr(2) is bonded to one O(1), one O(10), one O(11), one O(4), one O(6), 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, corners with two equivalent Si(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent O(1) and two equivalent O(9) atoms to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-48°. In the second Si site, Si(2) is bonded to two equivalent O(10) and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. In the third Si site, Si(3) is bonded to one O(12), one O(4), one O(6), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. P(1) is bonded to one O(11), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-40°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(3), one Zr(2), and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Zr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zr(2), and one Si(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Zr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(4), two equivalent Na(3), one Zr(2), and one Si(3) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(1), one Zr(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Zr(1), and one Si(3) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Zr(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zr(2), and one Si(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Zr(2), 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(3), one Zr(1), and one Si(3) atom.
Na3Zr2Si2PO12 crystallizes in the monoclinic C2 space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent O(12), two equivalent O(3), two equivalent O(7), and two equivalent O(9) atoms. Both Na(1)-O(12) bond lengths are 2.57 Å. Both Na(1)-O(3) bond lengths are 2.51 Å. Both Na(1)-O(7) bond lengths are 2.83 Å. Both Na(1)-O(9) bond lengths are 2.46 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(10), two equivalent O(11), two equivalent O(4), and two equivalent O(8) atoms. Both Na(2)-O(10) bond lengths are 2.64 Å. Both Na(2)-O(11) bond lengths are 2.56 Å. Both Na(2)-O(4) bond lengths are 2.58 Å. Both Na(2)-O(8) bond lengths are 2.67 Å. In the third Na site, Na(3) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(12), one O(4), and two equivalent O(6) atoms. The Na(3)-O(1) bond length is 2.36 Å. The Na(3)-O(10) bond length is 2.72 Å. The Na(3)-O(12) bond length is 2.64 Å. The Na(3)-O(4) bond length is 2.51 Å. There is one shorter (2.40 Å) and one longer (2.77 Å) Na(3)-O(6) bond length. In the fourth Na site, Na(4) is bonded in a 6-coordinate geometry to one O(10), one O(3), one O(4), one O(5), one O(6), and one O(9) atom. The Na(4)-O(10) bond length is 2.46 Å. The Na(4)-O(3) bond length is 2.52 Å. The Na(4)-O(4) bond length is 2.83 Å. The Na(4)-O(5) bond length is 2.52 Å. The Na(4)-O(6) bond length is 2.98 Å. The Na(4)-O(9) bond length is 2.52 Å. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one O(12), one O(2), one O(3), one O(5), 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, corners with two equivalent Si(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Zr(1)-O(12) bond length is 2.10 Å. The Zr(1)-O(2) bond length is 2.00 Å. The Zr(1)-O(3) bond length is 2.25 Å. The Zr(1)-O(5) bond length is 2.18 Å. The Zr(1)-O(8) bond length is 2.06 Å. The Zr(1)-O(9) bond length is 2.14 Å. In the second Zr site, Zr(2) is bonded to one O(1), one O(10), one O(11), one O(4), one O(6), 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, corners with two equivalent Si(3)O4 tetrahedra, and corners with two equivalent P(1)O4 tetrahedra. The Zr(2)-O(1) bond length is 2.04 Å. The Zr(2)-O(10) bond length is 2.13 Å. The Zr(2)-O(11) bond length is 2.17 Å. The Zr(2)-O(4) bond length is 2.15 Å. The Zr(2)-O(6) bond length is 2.07 Å. The Zr(2)-O(7) bond length is 2.11 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to two equivalent O(1) and two equivalent O(9) atoms to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-48°. Both Si(1)-O(1) bond lengths are 1.65 Å. Both Si(1)-O(9) bond lengths are 1.65 Å. In the second Si site, Si(2) is bonded to two equivalent O(10) and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. Both Si(2)-O(10) bond lengths are 1.65 Å. Both Si(2)-O(2) bond lengths are 1.63 Å. In the third Si site, Si(3) is bonded to one O(12), one O(4), one O(6), and one O(8) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-42°. The Si(3)-O(12) bond length is 1.65 Å. The Si(3)-O(4) bond length is 1.64 Å. The Si(3)-O(6) bond length is 1.64 Å. The Si(3)-O(8) bond length is 1.63 Å. P(1) is bonded to one O(11), one O(3), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Zr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 18-40°. The P(1)-O(11) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(5) bond length is 1.54 Å. The P(1)-O(7) bond length is 1.56 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Na(3), one Zr(2), and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(2) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Zr(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zr(2), and one Si(3) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Na(4), one Zr(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 5-coordinate geometry to one Na(4), two equivalent Na(3), one Zr(2), and one Si(3) atom. In the seventh O site, O(7) is bonded in a 2-coordinate geometry to one Na(1), one Zr(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Zr(1), and one Si(3) atom. In the ninth O site, O(9) is bonded in a distorted rectangular see-saw-like geometry to one Na(1), one Na(4), one Zr(1), and one Si(1) atom. In the tenth O site, O(10) is bonded in a 5-coordinate geometry to one Na(2), one Na(3), one Na(4), one Zr(2), and one Si(2) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Na(2), one Zr(2), 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(3), one Zr(1), and one Si(3) atom.