Rb4N2O7 crystallizes in the triclinic P1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to two equivalent N(1), one O(2), one O(3), and three equivalent O(1) atoms. In the second Rb site, Rb(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted RbO6 octahedra that share corners with two equivalent Rb(2)O6 octahedra, corners with four equivalent Rb(3)O7 pentagonal bipyramids, edges with two equivalent Rb(2)O6 octahedra, and  an edgeedge with one Rb(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 71°. In the third Rb site, Rb(3) is bonded to one O(7), three equivalent O(4), and three equivalent O(5) atoms to form distorted RbO7 pentagonal bipyramids that share corners with four equivalent Rb(2)O6 octahedra,  a cornercorner with one O(6)Rb3O tetrahedra,  an edgeedge with one Rb(2)O6 octahedra, and edges with six equivalent Rb(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 23-88°. In the fourth Rb site, Rb(4) is bonded in a distorted hexagonal planar geometry to one N(2), two equivalent O(1), and three equivalent O(6) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Rb(1), one O(2), and one O(3) atom. In the second N site, N(2) is bonded in a distorted water-like geometry to one Rb(4), one O(4), and one O(7) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Rb(4) and three equivalent Rb(1) atoms to form distorted ORb5 trigonal bipyramids that share corners with four equivalent O(6)Rb3O tetrahedra, corners with four equivalent O(1)Rb5 trigonal bipyramids,  an edgeedge with one O(6)Rb3O tetrahedra, and edges with two equivalent O(1)Rb5 trigonal bipyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Rb(1), two equivalent Rb(2), and one N(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Rb(1), two equivalent Rb(2), and one N(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to three equivalent Rb(3) and one N(2) atom. In the fifth O site, O(5) is bonded to two equivalent Rb(2) and three equivalent Rb(3) atoms to form a mixture of distorted edge and corner-sharing ORb5 trigonal bipyramids. In the sixth O site, O(6) is bonded to three equivalent Rb(4) and one O(7) atom to form ORb3O tetrahedra that share  a cornercorner with one Rb(3)O7 pentagonal bipyramid, corners with six equivalent O(6)Rb3O tetrahedra, corners with four equivalent O(1)Rb5 trigonal bipyramids, and  an edgeedge with one O(1)Rb5 trigonal bipyramid. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Rb(3), one N(2), and one O(6) atom.
Rb4N2O7 crystallizes in the triclinic P1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to two equivalent N(1), one O(2), one O(3), and three equivalent O(1) atoms. There is one shorter (3.14 Å) and one longer (3.23 Å) Rb(1)-N(1) bond length. The Rb(1)-O(2) bond length is 2.89 Å. The Rb(1)-O(3) bond length is 3.29 Å. There are a spread of Rb(1)-O(1) bond distances ranging from 2.85-3.10 Å. In the second Rb site, Rb(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form distorted RbO6 octahedra that share corners with two equivalent Rb(2)O6 octahedra, corners with four equivalent Rb(3)O7 pentagonal bipyramids, edges with two equivalent Rb(2)O6 octahedra, and  an edgeedge with one Rb(3)O7 pentagonal bipyramid. The corner-sharing octahedral tilt angles are 71°. There is one shorter (2.88 Å) and one longer (3.19 Å) Rb(2)-O(2) bond length. There is one shorter (2.83 Å) and one longer (2.98 Å) Rb(2)-O(3) bond length. There is one shorter (2.88 Å) and one longer (2.89 Å) Rb(2)-O(5) bond length. In the third Rb site, Rb(3) is bonded to one O(7), three equivalent O(4), and three equivalent O(5) atoms to form distorted RbO7 pentagonal bipyramids that share corners with four equivalent Rb(2)O6 octahedra,  a cornercorner with one O(6)Rb3O tetrahedra,  an edgeedge with one Rb(2)O6 octahedra, and edges with six equivalent Rb(3)O7 pentagonal bipyramids. The corner-sharing octahedral tilt angles range from 23-88°. The Rb(3)-O(7) bond length is 3.29 Å. There are a spread of Rb(3)-O(4) bond distances ranging from 3.02-3.17 Å. There are a spread of Rb(3)-O(5) bond distances ranging from 2.91-3.13 Å. In the fourth Rb site, Rb(4) is bonded in a distorted hexagonal planar geometry to one N(2), two equivalent O(1), and three equivalent O(6) atoms. The Rb(4)-N(2) bond length is 3.16 Å. There is one shorter (2.77 Å) and one longer (3.06 Å) Rb(4)-O(1) bond length. There are a spread of Rb(4)-O(6) bond distances ranging from 2.86-3.13 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 120 degrees geometry to two equivalent Rb(1), one O(2), and one O(3) atom. The N(1)-O(2) bond length is 1.27 Å. The N(1)-O(3) bond length is 1.27 Å. In the second N site, N(2) is bonded in a distorted water-like geometry to one Rb(4), one O(4), and one O(7) atom. The N(2)-O(4) bond length is 1.24 Å. The N(2)-O(7) bond length is 1.39 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Rb(4) and three equivalent Rb(1) atoms to form distorted ORb5 trigonal bipyramids that share corners with four equivalent O(6)Rb3O tetrahedra, corners with four equivalent O(1)Rb5 trigonal bipyramids,  an edgeedge with one O(6)Rb3O tetrahedra, and edges with two equivalent O(1)Rb5 trigonal bipyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Rb(1), two equivalent Rb(2), and one N(1) atom. In the third O site, O(3) is bonded in a 1-coordinate geometry to one Rb(1), two equivalent Rb(2), and one N(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to three equivalent Rb(3) and one N(2) atom. In the fifth O site, O(5) is bonded to two equivalent Rb(2) and three equivalent Rb(3) atoms to form a mixture of distorted edge and corner-sharing ORb5 trigonal bipyramids. In the sixth O site, O(6) is bonded to three equivalent Rb(4) and one O(7) atom to form ORb3O tetrahedra that share  a cornercorner with one Rb(3)O7 pentagonal bipyramid, corners with six equivalent O(6)Rb3O tetrahedra, corners with four equivalent O(1)Rb5 trigonal bipyramids, and  an edgeedge with one O(1)Rb5 trigonal bipyramid. The O(6)-O(7) bond length is 1.39 Å. In the seventh O site, O(7) is bonded in a distorted single-bond geometry to one Rb(3), one N(2), and one O(6) atom.