Na5(AsO8)2O2 crystallizes in the monoclinic P2/c space group. The structure consists of two hydrogen peroxide molecules inside a Na5(AsO8)2 framework. In the Na5(AsO8)2 framework, there are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(8) atoms. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(6), one O(8), and two equivalent O(5) atoms. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(2), one O(5), one O(7), and two equivalent O(10) atoms. As(1) is bonded to one O(10), one O(4), one O(8), and one O(9) atom to form corner-sharing AsO4 tetrahedra. There are nine inequivalent O sites. In the first O site, O(6) is bonded in a distorted linear geometry to two equivalent Na(2) and two equivalent O(3) atoms. In the second O site, O(7) is bonded in a bent 120 degrees geometry to one Na(3) and one O(3) atom. In the third O site, O(8) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one As(1) atom. In the fourth O site, O(9) is bonded in a single-bond geometry to one As(1) atom. In the fifth O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one As(1) atom. In the sixth O site, O(2) is bonded in a water-like geometry to one Na(3) and one O(2) atom. In the seventh O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one O(6), and one O(7) atom. In the eighth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to two equivalent Na(2) and two equivalent As(1) atoms. In the ninth O site, O(5) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(2), and one O(5) atom.
Na5(AsO8)2O2 crystallizes in the monoclinic P2/c space group. The structure consists of two hydrogen peroxide molecules inside a Na5(AsO8)2 framework. In the Na5(AsO8)2 framework, there are three inequivalent Na sites. In the first Na site, Na(1) is bonded in a square co-planar geometry to two equivalent O(3) and two equivalent O(8) atoms. Both Na(1)-O(3) bond lengths are 2.60 Å. Both Na(1)-O(8) bond lengths are 2.37 Å. In the second Na site, Na(2) is bonded in a 6-coordinate geometry to one O(3), one O(4), one O(6), one O(8), and two equivalent O(5) atoms. The Na(2)-O(3) bond length is 2.84 Å. The Na(2)-O(4) bond length is 2.37 Å. The Na(2)-O(6) bond length is 2.27 Å. The Na(2)-O(8) bond length is 2.28 Å. There is one shorter (2.59 Å) and one longer (2.67 Å) Na(2)-O(5) bond length. In the third Na site, Na(3) is bonded in a 3-coordinate geometry to one O(2), one O(5), one O(7), and two equivalent O(10) atoms. The Na(3)-O(2) bond length is 2.97 Å. The Na(3)-O(5) bond length is 3.00 Å. The Na(3)-O(7) bond length is 2.36 Å. There is one shorter (2.23 Å) and one longer (2.29 Å) Na(3)-O(10) bond length. As(1) is bonded to one O(10), one O(4), one O(8), and one O(9) atom to form corner-sharing AsO4 tetrahedra. The As(1)-O(10) bond length is 1.71 Å. The As(1)-O(4) bond length is 1.88 Å. The As(1)-O(8) bond length is 1.72 Å. The As(1)-O(9) bond length is 1.69 Å. There are nine inequivalent O sites. In the first O site, O(6) is bonded in a distorted linear geometry to two equivalent Na(2) and two equivalent O(3) atoms. Both O(6)-O(3) bond lengths are 1.86 Å. In the second O site, O(7) is bonded in a bent 120 degrees geometry to one Na(3) and one O(3) atom. The O(7)-O(3) bond length is 1.26 Å. In the third O site, O(8) is bonded in a distorted T-shaped geometry to one Na(1), one Na(2), and one As(1) atom. In the fourth O site, O(9) is bonded in a single-bond geometry to one As(1) atom. In the fifth O site, O(10) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one As(1) atom. In the sixth O site, O(2) is bonded in a water-like geometry to one Na(3) and one O(2) atom. The O(2)-O(2) bond length is 1.23 Å. In the seventh O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one O(6), and one O(7) atom. In the eighth O site, O(4) is bonded in a distorted trigonal pyramidal geometry to two equivalent Na(2) and two equivalent As(1) atoms. In the ninth O site, O(5) is bonded in a 4-coordinate geometry to one Na(3), two equivalent Na(2), and one O(5) atom. The O(5)-O(5) bond length is 1.27 Å.