Cs5Na(W2N5)2 crystallizes in the tetragonal I4_1 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to one N(1), one N(2), one N(4), and one N(5) atom. In the third Cs site, Cs(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. Na(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted NaN4 tetrahedra that share corners with two equivalent W(1)N4 tetrahedra and corners with two equivalent W(2)N4 tetrahedra. 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 WN4 tetrahedra that share  a cornercorner with one Na(1)N4 tetrahedra,  a cornercorner with one W(2)N4 tetrahedra, and corners with two equivalent W(1)N4 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 WN4 tetrahedra that share  a cornercorner with one Na(1)N4 tetrahedra,  a cornercorner with one W(1)N4 tetrahedra, and corners with two equivalent W(2)N4 tetrahedra. There are five inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 150 degrees geometry to one Cs(2), two equivalent Cs(1), one Na(1), and one W(1) atom. In the second N site, N(2) is bonded in a distorted linear geometry to one Cs(2), one Cs(3), two equivalent Cs(1), one Na(1), and one W(2) atom. In the third N site, N(3) is bonded in a distorted linear geometry to one Cs(3), two equivalent Cs(1), and two equivalent W(1) atoms. In the fourth N site, N(4) is bonded in a linear geometry to one Cs(2), one Cs(3), and two equivalent W(2) atoms. In the fifth N site, N(5) is bonded in a distorted bent 150 degrees geometry to one Cs(2), one Cs(3), one W(1), and one W(2) atom.
Cs5Na(W2N5)2 crystallizes in the tetragonal I4_1 space group. There are three inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 6-coordinate geometry to two equivalent N(1), two equivalent N(2), and two equivalent N(3) atoms. There is one shorter (3.23 Å) and one longer (3.51 Å) Cs(1)-N(1) bond length. There is one shorter (3.24 Å) and one longer (3.69 Å) Cs(1)-N(2) bond length. There is one shorter (3.55 Å) and one longer (3.57 Å) Cs(1)-N(3) bond length. In the second Cs site, Cs(2) is bonded in a 4-coordinate geometry to one N(1), one N(2), one N(4), and one N(5) atom. The Cs(2)-N(1) bond length is 3.24 Å. The Cs(2)-N(2) bond length is 3.36 Å. The Cs(2)-N(4) bond length is 3.57 Å. The Cs(2)-N(5) bond length is 3.35 Å. In the third Cs site, Cs(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 Cs(3)-N(2) bond lengths are 3.56 Å. Both Cs(3)-N(3) bond lengths are 3.62 Å. Both Cs(3)-N(4) bond lengths are 3.74 Å. Both Cs(3)-N(5) bond lengths are 3.48 Å. Na(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form distorted NaN4 tetrahedra that share corners with two equivalent W(1)N4 tetrahedra and corners with two equivalent W(2)N4 tetrahedra. Both Na(1)-N(1) bond lengths are 2.34 Å. Both Na(1)-N(2) bond lengths are 2.32 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 WN4 tetrahedra that share  a cornercorner with one Na(1)N4 tetrahedra,  a cornercorner with one W(2)N4 tetrahedra, and corners with two equivalent W(1)N4 tetrahedra. The W(1)-N(1) bond length is 1.79 Å. The W(1)-N(5) bond length is 1.91 Å. There is one shorter (1.91 Å) and one longer (1.93 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 WN4 tetrahedra that share  a cornercorner with one Na(1)N4 tetrahedra,  a cornercorner with one W(1)N4 tetrahedra, and corners with two equivalent W(2)N4 tetrahedra. The W(2)-N(2) bond length is 1.79 Å. The W(2)-N(5) bond length is 1.92 Å. There is one shorter (1.89 Å) and one longer (1.91 Å) W(2)-N(4) bond length. There are five inequivalent N sites. In the first N site, N(1) is bonded in a distorted bent 150 degrees geometry to one Cs(2), two equivalent Cs(1), one Na(1), and one W(1) atom. In the second N site, N(2) is bonded in a distorted linear geometry to one Cs(2), one Cs(3), two equivalent Cs(1), one Na(1), and one W(2) atom. In the third N site, N(3) is bonded in a distorted linear geometry to one Cs(3), two equivalent Cs(1), and two equivalent W(1) atoms. In the fourth N site, N(4) is bonded in a linear geometry to one Cs(2), one Cs(3), and two equivalent W(2) atoms. In the fifth N site, N(5) is bonded in a distorted bent 150 degrees geometry to one Cs(2), one Cs(3), one W(1), and one W(2) atom.