NaZrSi2O7 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(6) atoms. Zr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form ZrO6 octahedra that share corners with three equivalent Si(1)O4 tetrahedra and corners with three equivalent Si(2)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form SiO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-42°. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form SiO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-48°. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Zr(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(2) atom.
NaZrSi2O7 crystallizes in the triclinic P-1 space group. Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(2), one O(3), and two equivalent O(6) atoms. The Na(1)-O(1) bond length is 2.39 Å. The Na(1)-O(2) bond length is 2.48 Å. The Na(1)-O(3) bond length is 2.48 Å. There is one shorter (2.48 Å) and one longer (2.86 Å) Na(1)-O(6) bond length. Zr(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form ZrO6 octahedra that share corners with three equivalent Si(1)O4 tetrahedra and corners with three equivalent Si(2)O4 tetrahedra. The Zr(1)-O(1) bond length is 2.15 Å. The Zr(1)-O(2) bond length is 2.16 Å. The Zr(1)-O(3) bond length is 2.11 Å. The Zr(1)-O(4) bond length is 2.04 Å. The Zr(1)-O(5) bond length is 2.09 Å. The Zr(1)-O(6) bond length is 2.14 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form SiO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 25-42°. The Si(1)-O(2) bond length is 1.65 Å. The Si(1)-O(3) bond length is 1.63 Å. The Si(1)-O(5) bond length is 1.63 Å. The Si(1)-O(7) bond length is 1.65 Å. In the second Si site, Si(2) is bonded to one O(1), one O(4), one O(6), and one O(7) atom to form SiO4 tetrahedra that share corners with three equivalent Zr(1)O6 octahedra and  a cornercorner with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-48°. The Si(2)-O(1) bond length is 1.64 Å. The Si(2)-O(4) bond length is 1.63 Å. The Si(2)-O(6) bond length is 1.64 Å. The Si(2)-O(7) bond length is 1.65 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(2) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Zr(1) and one Si(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to two equivalent Na(1), one Zr(1), and one Si(2) atom. In the seventh O site, O(7) is bonded in a bent 120 degrees geometry to one Si(1) and one Si(2) atom.