Na3Zr(SiO3)6 crystallizes in the monoclinic C2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(4), one O(6), two equivalent O(10), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO8 hexagonal bipyramids that share corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Zr(1)O6 octahedra, edges with two equivalent Si(1)O4 tetrahedra, and edges with two equivalent Si(3)O4 tetrahedra. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. Zr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and edges with two equivalent Na(1)O8 hexagonal bipyramids. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(3), one O(6), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles are 33°. In the second Si site, Si(2) is bonded to one O(1), one O(10), one O(7), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 18°. In the third Si site, Si(3) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles are 31°. There are ten inequivalent O sites. In the first O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one Si(1) atom. In the second O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Si(1), and one Si(2) atom. In the third O site, O(10) is bonded in a bent 120 degrees geometry to one Na(1) and one Si(2) atom. In the fourth O site, O(1) is bonded in a 2-coordinate geometry to one Na(2), one Zr(1), and one Si(2) atom. In the fifth O site, O(2) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Zr(1), and one Si(3) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zr(1), and one Si(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Si(3) atoms. In the eighth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one Si(3) atom. In the ninth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent Si(1) atoms. In the tenth O site, O(7) is bonded in a distorted T-shaped geometry to one Na(2), one Si(2), and one Si(3) atom.
Na3Zr(SiO3)6 crystallizes in the monoclinic C2 space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(4), one O(6), two equivalent O(10), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO8 hexagonal bipyramids that share corners with two equivalent Si(2)O4 tetrahedra, edges with two equivalent Zr(1)O6 octahedra, edges with two equivalent Si(1)O4 tetrahedra, and edges with two equivalent Si(3)O4 tetrahedra. The Na(1)-O(4) bond length is 2.47 Å. The Na(1)-O(6) bond length is 2.55 Å. Both Na(1)-O(10) bond lengths are 2.64 Å. Both Na(1)-O(2) bond lengths are 2.93 Å. Both Na(1)-O(3) bond lengths are 2.78 Å. In the second Na site, Na(2) is bonded in a 7-coordinate geometry to one O(1), one O(2), one O(3), one O(5), one O(7), one O(8), and one O(9) atom. The Na(2)-O(1) bond length is 2.77 Å. The Na(2)-O(2) bond length is 2.73 Å. The Na(2)-O(3) bond length is 2.67 Å. The Na(2)-O(5) bond length is 2.36 Å. The Na(2)-O(7) bond length is 2.57 Å. The Na(2)-O(8) bond length is 2.38 Å. The Na(2)-O(9) bond length is 2.56 Å. Zr(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form ZrO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, corners with two equivalent Si(3)O4 tetrahedra, and edges with two equivalent Na(1)O8 hexagonal bipyramids. Both Zr(1)-O(1) bond lengths are 2.08 Å. Both Zr(1)-O(2) bond lengths are 2.10 Å. Both Zr(1)-O(3) bond lengths are 2.14 Å. There are three inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(3), one O(6), one O(8), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles are 33°. The Si(1)-O(3) bond length is 1.62 Å. The Si(1)-O(6) bond length is 1.63 Å. The Si(1)-O(8) bond length is 1.63 Å. The Si(1)-O(9) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(1), one O(10), one O(7), and one O(9) atom to form SiO4 tetrahedra that share  a cornercorner with one Na(1)O8 hexagonal bipyramid,  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 18°. The Si(2)-O(1) bond length is 1.61 Å. The Si(2)-O(10) bond length is 1.64 Å. The Si(2)-O(7) bond length is 1.64 Å. The Si(2)-O(9) bond length is 1.64 Å. In the third Si site, Si(3) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form SiO4 tetrahedra that share  a cornercorner with one Zr(1)O6 octahedra,  a cornercorner with one Si(2)O4 tetrahedra,  a cornercorner with one Si(3)O4 tetrahedra, and  an edgeedge with one Na(1)O8 hexagonal bipyramid. The corner-sharing octahedral tilt angles are 31°. The Si(3)-O(2) bond length is 1.62 Å. The Si(3)-O(4) bond length is 1.64 Å. The Si(3)-O(5) bond length is 1.62 Å. The Si(3)-O(7) bond length is 1.63 Å. There are ten inequivalent O sites. In the first O site, O(8) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one Si(1) atom. In the second O site, O(9) is bonded in a 3-coordinate geometry to one Na(2), one Si(1), and one Si(2) atom. In the third O site, O(10) is bonded in a bent 120 degrees geometry to one Na(1) and one Si(2) atom. In the fourth O site, O(1) is bonded in a 2-coordinate geometry to one Na(2), one Zr(1), and one Si(2) atom. In the fifth O site, O(2) is bonded in a 2-coordinate geometry to one Na(1), one Na(2), one Zr(1), and one Si(3) atom. In the sixth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one Zr(1), and one Si(1) atom. In the seventh O site, O(4) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Si(3) atoms. In the eighth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Na(2) and one Si(3) atom. In the ninth O site, O(6) is bonded in a distorted T-shaped geometry to one Na(1) and two equivalent Si(1) atoms. In the tenth O site, O(7) is bonded in a distorted T-shaped geometry to one Na(2), one Si(2), and one Si(3) atom.