RbSmGeSe4 crystallizes in the orthorhombic P2_12_12_1 space group. Rb(1) is bonded in a 8-coordinate geometry to one Se(1), two equivalent Se(2), two equivalent Se(4), and three equivalent Se(3) atoms. Sm(1) is bonded in a 7-coordinate geometry to one Se(3), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(4) atoms. Ge(1) is bonded in a tetrahedral geometry to one Se(1), one Se(2), one Se(3), and one Se(4) atom. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted see-saw-like geometry to one Rb(1), two equivalent Sm(1), and one Ge(1) atom. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Sm(1), and one Ge(1) atom. In the third Se site, Se(3) is bonded to three equivalent Rb(1), one Sm(1), and one Ge(1) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the fourth Se site, Se(4) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Sm(1), and one Ge(1) atom.
RbSmGeSe4 crystallizes in the orthorhombic P2_12_12_1 space group. Rb(1) is bonded in a 8-coordinate geometry to one Se(1), two equivalent Se(2), two equivalent Se(4), and three equivalent Se(3) atoms. The Rb(1)-Se(1) bond length is 3.45 Å. There is one shorter (3.67 Å) and one longer (4.01 Å) Rb(1)-Se(2) bond length. Both Rb(1)-Se(4) bond lengths are 3.82 Å. There are a spread of Rb(1)-Se(3) bond distances ranging from 3.61-3.78 Å. Sm(1) is bonded in a 7-coordinate geometry to one Se(3), two equivalent Se(1), two equivalent Se(2), and two equivalent Se(4) atoms. The Sm(1)-Se(3) bond length is 3.01 Å. There is one shorter (2.99 Å) and one longer (3.12 Å) Sm(1)-Se(1) bond length. Both Sm(1)-Se(2) bond lengths are 3.06 Å. There is one shorter (3.02 Å) and one longer (3.04 Å) Sm(1)-Se(4) bond length. Ge(1) is bonded in a tetrahedral geometry to one Se(1), one Se(2), one Se(3), and one Se(4) atom. The Ge(1)-Se(1) bond length is 2.38 Å. The Ge(1)-Se(2) bond length is 2.39 Å. The Ge(1)-Se(3) bond length is 2.36 Å. The Ge(1)-Se(4) bond length is 2.39 Å. There are four inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted see-saw-like geometry to one Rb(1), two equivalent Sm(1), and one Ge(1) atom. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Sm(1), and one Ge(1) atom. In the third Se site, Se(3) is bonded to three equivalent Rb(1), one Sm(1), and one Ge(1) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the fourth Se site, Se(4) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Sm(1), and one Ge(1) atom.