Rb3W2N5 crystallizes in the tetragonal I4_1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to one N(1), one N(4), two equivalent N(2), and two equivalent N(3) atoms. In the second Rb site, Rb(2) is bonded in a 5-coordinate geometry to one N(1), two equivalent N(4), and two equivalent N(5) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to two equivalent N(2), two equivalent N(3), two equivalent N(4), and two equivalent N(5) atoms. In the fourth Rb site, Rb(4) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded to one N(1), one N(5), and two equivalent N(3) atoms to form corner-sharing WN4 tetrahedra. In the second W site, W(2) is bonded to one N(2), one N(5), and two equivalent N(4) atoms to form corner-sharing WN4 tetrahedra. There are five inequivalent N sites. In the first N site, N(1) is bonded to one Rb(1), one Rb(2), one Rb(4), and one W(1) atom to form distorted corner-sharing NRb3W trigonal pyramids. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Rb(3), one Rb(4), two equivalent Rb(1), and one W(2) atom. In the third N site, N(3) is bonded in a 2-coordinate geometry to one Rb(3), two equivalent Rb(1), and two equivalent W(1) atoms. In the fourth N site, N(4) is bonded in a distorted linear geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and two equivalent W(2) atoms. In the fifth N site, N(5) is bonded in a 5-coordinate geometry to one Rb(3), two equivalent Rb(2), one W(1), and one W(2) atom.
Rb3W2N5 crystallizes in the tetragonal I4_1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 6-coordinate geometry to one N(1), one N(4), two equivalent N(2), and two equivalent N(3) atoms. The Rb(1)-N(1) bond length is 2.88 Å. The Rb(1)-N(4) bond length is 3.55 Å. There is one shorter (3.13 Å) and one longer (3.14 Å) Rb(1)-N(2) bond length. There is one shorter (3.03 Å) and one longer (3.36 Å) Rb(1)-N(3) bond length. In the second Rb site, Rb(2) is bonded in a 5-coordinate geometry to one N(1), two equivalent N(4), and two equivalent N(5) atoms. The Rb(2)-N(1) bond length is 2.83 Å. There is one shorter (3.34 Å) and one longer (3.52 Å) Rb(2)-N(4) bond length. There is one shorter (3.05 Å) and one longer (3.15 Å) Rb(2)-N(5) bond length. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to two equivalent N(2), two equivalent N(3), two equivalent N(4), and two equivalent N(5) atoms. Both Rb(3)-N(2) bond lengths are 3.10 Å. Both Rb(3)-N(3) bond lengths are 3.45 Å. Both Rb(3)-N(4) bond lengths are 3.42 Å. Both Rb(3)-N(5) bond lengths are 3.15 Å. In the fourth Rb site, Rb(4) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Rb(4)-N(1) bond lengths are 2.83 Å. Both Rb(4)-N(2) bond lengths are 2.90 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded to one N(1), one N(5), and two equivalent N(3) atoms to form corner-sharing WN4 tetrahedra. The W(1)-N(1) bond length is 1.78 Å. The W(1)-N(5) bond length is 1.95 Å. There is one shorter (1.91 Å) and one longer (1.92 Å) W(1)-N(3) bond length. In the second W site, W(2) is bonded to one N(2), one N(5), and two equivalent N(4) atoms to form corner-sharing WN4 tetrahedra. The W(2)-N(2) bond length is 1.78 Å. The W(2)-N(5) bond length is 1.93 Å. There is one shorter (1.92 Å) and one longer (1.93 Å) W(2)-N(4) bond length. There are five inequivalent N sites. In the first N site, N(1) is bonded to one Rb(1), one Rb(2), one Rb(4), and one W(1) atom to form distorted corner-sharing NRb3W trigonal pyramids. In the second N site, N(2) is bonded in a 5-coordinate geometry to one Rb(3), one Rb(4), two equivalent Rb(1), and one W(2) atom. In the third N site, N(3) is bonded in a 2-coordinate geometry to one Rb(3), two equivalent Rb(1), and two equivalent W(1) atoms. In the fourth N site, N(4) is bonded in a distorted linear geometry to one Rb(1), one Rb(3), two equivalent Rb(2), and two equivalent W(2) atoms. In the fifth N site, N(5) is bonded in a 5-coordinate geometry to one Rb(3), two equivalent Rb(2), one W(1), and one W(2) atom.