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 5-coordinate geometry to one N(1), one O(2), one O(3), and two 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 a mixture of distorted corner and edge-sharing RbO6 octahedra. The corner-sharing octahedral tilt angles are 70°. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(5), and two equivalent O(7) atoms. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one O(4), one O(7), 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 one Rb(1), one O(2), and one O(3) atom. In the second N site, N(2) is bonded in a trigonal planar geometry to one O(4), one O(6), and one O(7) atom. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Rb(1) and two equivalent Rb(4) atoms to form ORb4 tetrahedra that share corners with two equivalent O(2)Rb3N tetrahedra, corners with two equivalent O(3)Rb3N tetrahedra, and corners with four equivalent O(1)Rb4 tetrahedra. In the second O site, O(2) is bonded to one Rb(1), two equivalent Rb(2), and one N(1) atom to form distorted ORb3N tetrahedra that share corners with two equivalent O(2)Rb3N tetrahedra, corners with two equivalent O(3)Rb3N tetrahedra, corners with two equivalent O(1)Rb4 tetrahedra, corners with two equivalent O(5)Rb4 trigonal pyramids, edges with two equivalent O(3)Rb3N tetrahedra, and  an edgeedge with one O(5)Rb4 trigonal pyramid. In the third O site, O(3) is bonded to one Rb(1), two equivalent Rb(2), and one N(1) atom to form distorted ORb3N tetrahedra that share corners with two equivalent O(2)Rb3N tetrahedra, corners with two equivalent O(3)Rb3N tetrahedra, corners with two equivalent O(1)Rb4 tetrahedra, corners with four equivalent O(5)Rb4 trigonal pyramids, and edges with two equivalent O(2)Rb3N tetrahedra. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Rb(4), two equivalent Rb(3), and one N(2) atom. In the fifth O site, O(5) is bonded to two equivalent Rb(2) and two equivalent Rb(3) atoms to form ORb4 trigonal pyramids that share corners with two equivalent O(2)Rb3N tetrahedra, corners with four equivalent O(3)Rb3N tetrahedra, corners with four equivalent O(5)Rb4 trigonal pyramids, and  an edgeedge with one O(2)Rb3N tetrahedra. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to three equivalent Rb(4) and one N(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Rb(4), two equivalent Rb(3), and one N(2) 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 5-coordinate geometry to one N(1), one O(2), one O(3), and two equivalent O(1) atoms. The Rb(1)-N(1) bond length is 3.15 Å. The Rb(1)-O(2) bond length is 2.90 Å. The Rb(1)-O(3) bond length is 2.99 Å. There is one shorter (2.78 Å) and one longer (2.85 Å) Rb(1)-O(1) bond length. 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 a mixture of distorted corner and edge-sharing RbO6 octahedra. The corner-sharing octahedral tilt angles are 70°. There is one shorter (2.89 Å) and one longer (2.97 Å) Rb(2)-O(2) bond length. There is one shorter (2.91 Å) and one longer (3.08 Å) Rb(2)-O(3) bond length. There is one shorter (2.92 Å) and one longer (2.98 Å) Rb(2)-O(5) bond length. In the third Rb site, Rb(3) is bonded in a 6-coordinate geometry to two equivalent O(4), two equivalent O(5), and two equivalent O(7) atoms. There is one shorter (2.98 Å) and one longer (3.39 Å) Rb(3)-O(4) bond length. There is one shorter (2.89 Å) and one longer (2.90 Å) Rb(3)-O(5) bond length. There is one shorter (2.94 Å) and one longer (3.29 Å) Rb(3)-O(7) bond length. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one O(4), one O(7), two equivalent O(1), and three equivalent O(6) atoms. The Rb(4)-O(4) bond length is 3.11 Å. The Rb(4)-O(7) bond length is 3.04 Å. There is one shorter (2.84 Å) and one longer (2.90 Å) Rb(4)-O(1) bond length. There are a spread of Rb(4)-O(6) bond distances ranging from 2.97-3.08 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 120 degrees geometry to one 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 trigonal planar geometry to one O(4), one O(6), and one O(7) atom. The N(2)-O(4) bond length is 1.27 Å. The N(2)-O(6) bond length is 1.27 Å. The N(2)-O(7) bond length is 1.27 Å. There are seven inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Rb(1) and two equivalent Rb(4) atoms to form ORb4 tetrahedra that share corners with two equivalent O(2)Rb3N tetrahedra, corners with two equivalent O(3)Rb3N tetrahedra, and corners with four equivalent O(1)Rb4 tetrahedra. In the second O site, O(2) is bonded to one Rb(1), two equivalent Rb(2), and one N(1) atom to form distorted ORb3N tetrahedra that share corners with two equivalent O(2)Rb3N tetrahedra, corners with two equivalent O(3)Rb3N tetrahedra, corners with two equivalent O(1)Rb4 tetrahedra, corners with two equivalent O(5)Rb4 trigonal pyramids, edges with two equivalent O(3)Rb3N tetrahedra, and  an edgeedge with one O(5)Rb4 trigonal pyramid. In the third O site, O(3) is bonded to one Rb(1), two equivalent Rb(2), and one N(1) atom to form distorted ORb3N tetrahedra that share corners with two equivalent O(2)Rb3N tetrahedra, corners with two equivalent O(3)Rb3N tetrahedra, corners with two equivalent O(1)Rb4 tetrahedra, corners with four equivalent O(5)Rb4 trigonal pyramids, and edges with two equivalent O(2)Rb3N tetrahedra. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to one Rb(4), two equivalent Rb(3), and one N(2) atom. In the fifth O site, O(5) is bonded to two equivalent Rb(2) and two equivalent Rb(3) atoms to form ORb4 trigonal pyramids that share corners with two equivalent O(2)Rb3N tetrahedra, corners with four equivalent O(3)Rb3N tetrahedra, corners with four equivalent O(5)Rb4 trigonal pyramids, and  an edgeedge with one O(2)Rb3N tetrahedra. In the sixth O site, O(6) is bonded in a distorted single-bond geometry to three equivalent Rb(4) and one N(2) atom. In the seventh O site, O(7) is bonded in a 4-coordinate geometry to one Rb(4), two equivalent Rb(3), and one N(2) atom.