(Na2ZrSi6O15)2(O2)3 crystallizes in the orthorhombic Pma2 space group. The structure consists of two trioxidane molecules inside a Na2ZrSi6O15 framework. In the Na2ZrSi6O15 framework, there are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(7), and two equivalent O(5) atoms. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(8) atoms. Zr(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms to form ZrO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. There are three 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(6) 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  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. In the second Si site, Si(2) is bonded to one O(6), one O(7), 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  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 32°. In the third Si site, Si(3) is bonded to one O(3), one O(4), one O(5), 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  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 13°. There are nine inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the second O site, O(7) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Si(2) atoms. In the third O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Zr(1), and one Si(2) atom. In the fourth O site, O(9) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the fifth O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and two equivalent Si(1) atoms. In the sixth O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Zr(1), and one Si(1) atom. In the seventh O site, O(3) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the eighth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Si(3) atoms. In the ninth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(3) atom.
(Na2ZrSi6O15)2(O2)3 crystallizes in the orthorhombic Pma2 space group. The structure consists of two trioxidane molecules inside a Na2ZrSi6O15 framework. In the Na2ZrSi6O15 framework, there are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(7), and two equivalent O(5) atoms. The Na(1)-O(1) bond length is 2.76 Å. The Na(1)-O(4) bond length is 2.44 Å. The Na(1)-O(7) bond length is 2.46 Å. Both Na(1)-O(5) bond lengths are 2.70 Å. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to two equivalent O(2) and two equivalent O(8) atoms. Both Na(2)-O(2) bond lengths are 2.54 Å. Both Na(2)-O(8) bond lengths are 2.56 Å. Zr(1) is bonded to two equivalent O(2), two equivalent O(5), and two equivalent O(8) atoms to form ZrO6 octahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and corners with two equivalent Si(3)O4 tetrahedra. Both Zr(1)-O(2) bond lengths are 2.12 Å. Both Zr(1)-O(5) bond lengths are 2.08 Å. Both Zr(1)-O(8) bond lengths are 2.12 Å. There are three 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(6) 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  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.61 Å. The Si(1)-O(3) bond length is 1.64 Å. The Si(1)-O(6) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to one O(6), one O(7), 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  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 32°. The Si(2)-O(6) bond length is 1.62 Å. The Si(2)-O(7) bond length is 1.66 Å. The Si(2)-O(8) bond length is 1.61 Å. The Si(2)-O(9) bond length is 1.63 Å. In the third Si site, Si(3) is bonded to one O(3), one O(4), one O(5), 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  a cornercorner with one Si(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 13°. The Si(3)-O(3) bond length is 1.64 Å. The Si(3)-O(4) bond length is 1.65 Å. The Si(3)-O(5) bond length is 1.60 Å. The Si(3)-O(9) bond length is 1.63 Å. There are nine inequivalent O sites. In the first O site, O(6) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the second O site, O(7) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Si(2) atoms. In the third O site, O(8) is bonded in a 3-coordinate geometry to one Na(2), one Zr(1), and one Si(2) atom. In the fourth O site, O(9) is bonded in a bent 150 degrees geometry to one Si(2) and one Si(3) atom. In the fifth O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Na(1) and two equivalent Si(1) atoms. In the sixth O site, O(2) is bonded in a 3-coordinate geometry to one Na(2), one Zr(1), and one Si(1) atom. In the seventh O site, O(3) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(3) atom. In the eighth O site, O(4) is bonded in a 3-coordinate geometry to one Na(1) and two equivalent Si(3) atoms. In the ninth O site, O(5) is bonded in a 3-coordinate geometry to one Na(1), one Zr(1), and one Si(3) atom.