RbSmGeSe4 crystallizes in the triclinic P1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one Se(12), one Se(13), one Se(2), one Se(5), one Se(6), one Se(8), and two equivalent Se(11) atoms. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Se(1), one Se(14), one Se(16), one Se(3), one Se(4), one Se(7), and two equivalent Se(15) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Se(11), one Se(12), one Se(2), one Se(5), one Se(6), one Se(9), and two equivalent Se(13) atoms. In the fourth Rb site, Rb(4) is bonded in a 8-coordinate geometry to one Se(10), one Se(14), one Se(15), one Se(16), one Se(4), one Se(7), and two equivalent Se(3) atoms. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 7-coordinate geometry to one Se(10), one Se(12), one Se(16), one Se(3), one Se(4), one Se(5), and one Se(8) atom. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one Se(1), one Se(14), one Se(15), one Se(2), one Se(6), one Se(7), and one Se(9) atom. In the third Sm site, Sm(3) is bonded to one Se(10), one Se(11), one Se(12), one Se(16), one Se(4), one Se(5), and one Se(8) atom to form distorted SmSe7 pentagonal bipyramids that share  a cornercorner with one Ge(4)Se4 tetrahedra,  an edgeedge with one Ge(4)Se4 tetrahedra, and edges with two equivalent Ge(3)Se4 tetrahedra. In the fourth Sm site, Sm(4) is bonded in a 7-coordinate geometry to one Se(1), one Se(13), one Se(14), one Se(2), one Se(6), one Se(7), and one Se(9) atom. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a tetrahedral geometry to one Se(14), one Se(15), one Se(7), and one Se(9) atom. In the second Ge site, Ge(2) is bonded in a tetrahedral geometry to one Se(1), one Se(13), one Se(2), and one Se(6) atom. In the third Ge site, Ge(3) is bonded to one Se(10), one Se(11), one Se(12), and one Se(5) atom to form GeSe4 tetrahedra that share edges with two equivalent Sm(3)Se7 pentagonal bipyramids. In the fourth Ge site, Ge(4) is bonded to one Se(16), one Se(3), one Se(4), and one Se(8) atom to form GeSe4 tetrahedra that share  a cornercorner with one Sm(3)Se7 pentagonal bipyramid and  an edgeedge with one Sm(3)Se7 pentagonal bipyramid. There are sixteen inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted see-saw-like geometry to one Rb(2), one Sm(2), one Sm(4), and one Ge(2) atom. In the second Se site, Se(2) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(3), one Sm(2), one Sm(4), and one Ge(2) atom. In the third Se site, Se(3) is bonded to one Rb(2), two equivalent Rb(4), one Sm(1), and one Ge(4) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the fourth Se site, Se(4) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(1), one Sm(3), and one Ge(4) atom. In the fifth Se site, Se(5) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Sm(1), one Sm(3), and one Ge(3) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Sm(2), one Sm(4), and one Ge(2) atom. In the seventh Se site, Se(7) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(2), one Sm(4), and one Ge(1) atom. In the eighth Se site, Se(8) is bonded in a distorted see-saw-like geometry to one Rb(1), one Sm(1), one Sm(3), and one Ge(4) atom. In the ninth Se site, Se(9) is bonded in a distorted see-saw-like geometry to one Rb(3), one Sm(2), one Sm(4), and one Ge(1) atom. In the tenth Se site, Se(10) is bonded in a distorted see-saw-like geometry to one Rb(4), one Sm(1), one Sm(3), and one Ge(3) atom. In the eleventh Se site, Se(11) is bonded to one Rb(3), two equivalent Rb(1), one Sm(3), and one Ge(3) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the twelfth Se site, Se(12) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Sm(1), one Sm(3), and one Ge(3) atom. In the thirteenth Se site, Se(13) is bonded to one Rb(1), two equivalent Rb(3), one Sm(4), and one Ge(2) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the fourteenth Se site, Se(14) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(2), one Sm(4), and one Ge(1) atom. In the fifteenth Se site, Se(15) is bonded to one Rb(4), two equivalent Rb(2), one Sm(2), and one Ge(1) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the sixteenth Se site, Se(16) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(1), one Sm(3), and one Ge(4) atom.
RbSmGeSe4 crystallizes in the triclinic P1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 8-coordinate geometry to one Se(12), one Se(13), one Se(2), one Se(5), one Se(6), one Se(8), and two equivalent Se(11) atoms. The Rb(1)-Se(12) bond length is 3.78 Å. The Rb(1)-Se(13) bond length is 3.59 Å. The Rb(1)-Se(2) bond length is 3.70 Å. The Rb(1)-Se(5) bond length is 3.97 Å. The Rb(1)-Se(6) bond length is 3.81 Å. The Rb(1)-Se(8) bond length is 3.47 Å. Both Rb(1)-Se(11) bond lengths are 3.73 Å. In the second Rb site, Rb(2) is bonded in a 8-coordinate geometry to one Se(1), one Se(14), one Se(16), one Se(3), one Se(4), one Se(7), and two equivalent Se(15) atoms. The Rb(2)-Se(1) bond length is 3.42 Å. The Rb(2)-Se(14) bond length is 4.01 Å. The Rb(2)-Se(16) bond length is 3.72 Å. The Rb(2)-Se(3) bond length is 3.70 Å. The Rb(2)-Se(4) bond length is 3.85 Å. The Rb(2)-Se(7) bond length is 3.86 Å. There is one shorter (3.68 Å) and one longer (3.74 Å) Rb(2)-Se(15) bond length. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Se(11), one Se(12), one Se(2), one Se(5), one Se(6), one Se(9), and two equivalent Se(13) atoms. The Rb(3)-Se(11) bond length is 3.64 Å. The Rb(3)-Se(12) bond length is 3.82 Å. The Rb(3)-Se(2) bond length is 4.06 Å. The Rb(3)-Se(5) bond length is 3.69 Å. The Rb(3)-Se(6) bond length is 3.82 Å. The Rb(3)-Se(9) bond length is 3.41 Å. There is one shorter (3.67 Å) and one longer (3.77 Å) Rb(3)-Se(13) bond length. In the fourth Rb site, Rb(4) is bonded in a 8-coordinate geometry to one Se(10), one Se(14), one Se(15), one Se(16), one Se(4), one Se(7), and two equivalent Se(3) atoms. The Rb(4)-Se(10) bond length is 3.40 Å. The Rb(4)-Se(14) bond length is 3.71 Å. The Rb(4)-Se(15) bond length is 3.63 Å. The Rb(4)-Se(16) bond length is 4.05 Å. The Rb(4)-Se(4) bond length is 3.86 Å. The Rb(4)-Se(7) bond length is 3.89 Å. There is one shorter (3.63 Å) and one longer (3.81 Å) Rb(4)-Se(3) bond length. There are four inequivalent Sm sites. In the first Sm site, Sm(1) is bonded in a 7-coordinate geometry to one Se(10), one Se(12), one Se(16), one Se(3), one Se(4), one Se(5), and one Se(8) atom. The Sm(1)-Se(10) bond length is 3.10 Å. The Sm(1)-Se(12) bond length is 3.05 Å. The Sm(1)-Se(16) bond length is 3.04 Å. The Sm(1)-Se(3) bond length is 2.94 Å. The Sm(1)-Se(4) bond length is 3.04 Å. The Sm(1)-Se(5) bond length is 3.06 Å. The Sm(1)-Se(8) bond length is 2.93 Å. In the second Sm site, Sm(2) is bonded in a 7-coordinate geometry to one Se(1), one Se(14), one Se(15), one Se(2), one Se(6), one Se(7), and one Se(9) atom. The Sm(2)-Se(1) bond length is 3.06 Å. The Sm(2)-Se(14) bond length is 3.13 Å. The Sm(2)-Se(15) bond length is 3.01 Å. The Sm(2)-Se(2) bond length is 3.03 Å. The Sm(2)-Se(6) bond length is 3.06 Å. The Sm(2)-Se(7) bond length is 3.01 Å. The Sm(2)-Se(9) bond length is 3.00 Å. In the third Sm site, Sm(3) is bonded to one Se(10), one Se(11), one Se(12), one Se(16), one Se(4), one Se(5), and one Se(8) atom to form distorted SmSe7 pentagonal bipyramids that share  a cornercorner with one Ge(4)Se4 tetrahedra,  an edgeedge with one Ge(4)Se4 tetrahedra, and edges with two equivalent Ge(3)Se4 tetrahedra. The Sm(3)-Se(10) bond length is 2.98 Å. The Sm(3)-Se(11) bond length is 2.98 Å. The Sm(3)-Se(12) bond length is 3.04 Å. The Sm(3)-Se(16) bond length is 3.05 Å. The Sm(3)-Se(4) bond length is 3.06 Å. The Sm(3)-Se(5) bond length is 3.11 Å. The Sm(3)-Se(8) bond length is 3.09 Å. In the fourth Sm site, Sm(4) is bonded in a 7-coordinate geometry to one Se(1), one Se(13), one Se(14), one Se(2), one Se(6), one Se(7), and one Se(9) atom. The Sm(4)-Se(1) bond length is 3.07 Å. The Sm(4)-Se(13) bond length is 3.01 Å. The Sm(4)-Se(14) bond length is 3.06 Å. The Sm(4)-Se(2) bond length is 2.98 Å. The Sm(4)-Se(6) bond length is 3.05 Å. The Sm(4)-Se(7) bond length is 2.97 Å. The Sm(4)-Se(9) bond length is 3.18 Å. There are four inequivalent Ge sites. In the first Ge site, Ge(1) is bonded in a tetrahedral geometry to one Se(14), one Se(15), one Se(7), and one Se(9) atom. The Ge(1)-Se(14) bond length is 2.47 Å. The Ge(1)-Se(15) bond length is 2.36 Å. The Ge(1)-Se(7) bond length is 2.44 Å. The Ge(1)-Se(9) bond length is 2.39 Å. In the second Ge site, Ge(2) is bonded in a tetrahedral geometry to one Se(1), one Se(13), one Se(2), and one Se(6) atom. The Ge(2)-Se(1) bond length is 2.41 Å. The Ge(2)-Se(13) bond length is 2.35 Å. The Ge(2)-Se(2) bond length is 2.38 Å. The Ge(2)-Se(6) bond length is 2.34 Å. In the third Ge site, Ge(3) is bonded to one Se(10), one Se(11), one Se(12), and one Se(5) atom to form GeSe4 tetrahedra that share edges with two equivalent Sm(3)Se7 pentagonal bipyramids. The Ge(3)-Se(10) bond length is 2.40 Å. The Ge(3)-Se(11) bond length is 2.33 Å. The Ge(3)-Se(12) bond length is 2.48 Å. The Ge(3)-Se(5) bond length is 2.38 Å. In the fourth Ge site, Ge(4) is bonded to one Se(16), one Se(3), one Se(4), and one Se(8) atom to form GeSe4 tetrahedra that share  a cornercorner with one Sm(3)Se7 pentagonal bipyramid and  an edgeedge with one Sm(3)Se7 pentagonal bipyramid. The Ge(4)-Se(16) bond length is 2.39 Å. The Ge(4)-Se(3) bond length is 2.35 Å. The Ge(4)-Se(4) bond length is 2.46 Å. The Ge(4)-Se(8) bond length is 2.36 Å. There are sixteen inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted see-saw-like geometry to one Rb(2), one Sm(2), one Sm(4), and one Ge(2) atom. In the second Se site, Se(2) is bonded in a 3-coordinate geometry to one Rb(1), one Rb(3), one Sm(2), one Sm(4), and one Ge(2) atom. In the third Se site, Se(3) is bonded to one Rb(2), two equivalent Rb(4), one Sm(1), and one Ge(4) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the fourth Se site, Se(4) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(1), one Sm(3), and one Ge(4) atom. In the fifth Se site, Se(5) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Sm(1), one Sm(3), and one Ge(3) atom. In the sixth Se site, Se(6) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Sm(2), one Sm(4), and one Ge(2) atom. In the seventh Se site, Se(7) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(2), one Sm(4), and one Ge(1) atom. In the eighth Se site, Se(8) is bonded in a distorted see-saw-like geometry to one Rb(1), one Sm(1), one Sm(3), and one Ge(4) atom. In the ninth Se site, Se(9) is bonded in a distorted see-saw-like geometry to one Rb(3), one Sm(2), one Sm(4), and one Ge(1) atom. In the tenth Se site, Se(10) is bonded in a distorted see-saw-like geometry to one Rb(4), one Sm(1), one Sm(3), and one Ge(3) atom. In the eleventh Se site, Se(11) is bonded to one Rb(3), two equivalent Rb(1), one Sm(3), and one Ge(3) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the twelfth Se site, Se(12) is bonded in a 5-coordinate geometry to one Rb(1), one Rb(3), one Sm(1), one Sm(3), and one Ge(3) atom. In the thirteenth Se site, Se(13) is bonded to one Rb(1), two equivalent Rb(3), one Sm(4), and one Ge(2) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the fourteenth Se site, Se(14) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(2), one Sm(4), and one Ge(1) atom. In the fifteenth Se site, Se(15) is bonded to one Rb(4), two equivalent Rb(2), one Sm(2), and one Ge(1) atom to form distorted corner-sharing SeRb3SmGe trigonal bipyramids. In the sixteenth Se site, Se(16) is bonded in a 5-coordinate geometry to one Rb(2), one Rb(4), one Sm(1), one Sm(3), and one Ge(4) atom.