Na2ZrSi3O11 crystallizes in the monoclinic C2/c space group. Na(1) is bonded in a 4-coordinate geometry to one O(3), one O(4), one O(6), and one O(7) atom. Zr(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form ZrO6 octahedra that share corners with two equivalent Si(2)O4 tetrahedra and corners with four equivalent Si(1)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-26°. In the second Si site, Si(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 25°. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(1) atom. In the second O site, O(6) is bonded in a linear geometry to two equivalent Na(1) atoms. In the third O site, O(7) is bonded in a linear geometry to two equivalent Na(1) atoms. In the fourth O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Si(1) and one Si(2) atom. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Si(1) atoms. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Zr(1), and one Si(1) atom. In the seventh O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Zr(1), and one Si(2) atom.
Na2ZrSi3O11 crystallizes in the monoclinic C2/c space group. Na(1) is bonded in a 4-coordinate geometry to one O(3), one O(4), one O(6), and one O(7) atom. The Na(1)-O(3) bond length is 2.80 Å. The Na(1)-O(4) bond length is 2.82 Å. The Na(1)-O(6) bond length is 2.37 Å. The Na(1)-O(7) bond length is 2.36 Å. Zr(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(5) atoms to form ZrO6 octahedra that share corners with two equivalent Si(2)O4 tetrahedra and corners with four equivalent Si(1)O4 tetrahedra. Both Zr(1)-O(3) bond lengths are 2.10 Å. Both Zr(1)-O(4) bond lengths are 2.10 Å. Both Zr(1)-O(5) bond lengths are 2.11 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra, and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 21-26°. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.66 Å. The Si(1)-O(3) bond length is 1.62 Å. The Si(1)-O(5) bond length is 1.61 Å. In the second Si site, Si(2) is bonded to two equivalent O(1) and two equivalent O(4) atoms to form SiO4 tetrahedra that share corners with two equivalent Zr(1)O6 octahedra and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 25°. Both Si(2)-O(1) bond lengths are 1.67 Å. Both Si(2)-O(4) bond lengths are 1.61 Å. There are seven inequivalent O sites. In the first O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(1) atom. In the second O site, O(6) is bonded in a linear geometry to two equivalent Na(1) atoms. In the third O site, O(7) is bonded in a linear geometry to two equivalent Na(1) atoms. In the fourth O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Si(1) and one Si(2) atom. In the fifth O site, O(2) is bonded in a distorted bent 120 degrees geometry to two equivalent Si(1) atoms. In the sixth O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Zr(1), and one Si(1) atom. In the seventh O site, O(4) is bonded in a distorted bent 150 degrees geometry to one Na(1), one Zr(1), and one Si(2) atom.