Rb3GePSe7 crystallizes in the triclinic P-1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Se(3), one Se(4), one Se(7), two equivalent Se(1), and two equivalent Se(5) atoms. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one Se(2), one Se(4), one Se(5), one Se(6), two equivalent Se(3), and three equivalent Se(7) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to two equivalent Se(1), two equivalent Se(2), two equivalent Se(5), and two equivalent Se(6) atoms. Ge(1) is bonded to one Se(3), one Se(5), and two equivalent Se(4) atoms to form edge-sharing GeSe4 tetrahedra. P(1) is bonded in a tetrahedral geometry to one Se(1), one Se(2), one Se(6), and one Se(7) atom. There are seven inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(3), and one P(1) atom. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(3), one P(1), and one Se(3) atom. In the third Se site, Se(3) is bonded in a distorted single-bond geometry to one Rb(1), two equivalent Rb(2), one Ge(1), and one Se(2) atom. In the fourth Se site, Se(4) is bonded to one Rb(1), one Rb(2), and two equivalent Ge(1) atoms to form distorted edge-sharing SeRb2Ge2 trigonal pyramids. In the fifth Se site, Se(5) is bonded in a 6-coordinate geometry to one Rb(2), two equivalent Rb(1), two equivalent Rb(3), and one Ge(1) atom. In the sixth Se site, Se(6) is bonded in a 4-coordinate geometry to one Rb(2), two equivalent Rb(3), and one P(1) atom. In the seventh Se site, Se(7) is bonded in a 5-coordinate geometry to one Rb(1), three equivalent Rb(2), and one P(1) atom.
Rb3GePSe7 crystallizes in the triclinic P-1 space group. There are three inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 7-coordinate geometry to one Se(3), one Se(4), one Se(7), two equivalent Se(1), and two equivalent Se(5) atoms. The Rb(1)-Se(3) bond length is 3.79 Å. The Rb(1)-Se(4) bond length is 3.87 Å. The Rb(1)-Se(7) bond length is 3.46 Å. There is one shorter (3.65 Å) and one longer (3.66 Å) Rb(1)-Se(1) bond length. There is one shorter (3.65 Å) and one longer (3.81 Å) Rb(1)-Se(5) bond length. In the second Rb site, Rb(2) is bonded in a 9-coordinate geometry to one Se(2), one Se(4), one Se(5), one Se(6), two equivalent Se(3), and three equivalent Se(7) atoms. The Rb(2)-Se(2) bond length is 3.87 Å. The Rb(2)-Se(4) bond length is 3.57 Å. The Rb(2)-Se(5) bond length is 3.66 Å. The Rb(2)-Se(6) bond length is 3.55 Å. There is one shorter (3.85 Å) and one longer (3.94 Å) Rb(2)-Se(3) bond length. There are a spread of Rb(2)-Se(7) bond distances ranging from 3.54-3.79 Å. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to two equivalent Se(1), two equivalent Se(2), two equivalent Se(5), and two equivalent Se(6) atoms. There is one shorter (3.69 Å) and one longer (3.85 Å) Rb(3)-Se(1) bond length. There is one shorter (3.63 Å) and one longer (3.71 Å) Rb(3)-Se(2) bond length. There is one shorter (3.60 Å) and one longer (3.96 Å) Rb(3)-Se(5) bond length. There is one shorter (3.53 Å) and one longer (3.67 Å) Rb(3)-Se(6) bond length. Ge(1) is bonded to one Se(3), one Se(5), and two equivalent Se(4) atoms to form edge-sharing GeSe4 tetrahedra. The Ge(1)-Se(3) bond length is 2.45 Å. The Ge(1)-Se(5) bond length is 2.30 Å. There is one shorter (2.44 Å) and one longer (2.45 Å) Ge(1)-Se(4) bond length. P(1) is bonded in a tetrahedral geometry to one Se(1), one Se(2), one Se(6), and one Se(7) atom. The P(1)-Se(1) bond length is 2.22 Å. The P(1)-Se(2) bond length is 2.33 Å. The P(1)-Se(6) bond length is 2.19 Å. The P(1)-Se(7) bond length is 2.19 Å. There are seven inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to two equivalent Rb(1), two equivalent Rb(3), and one P(1) atom. In the second Se site, Se(2) is bonded in a 5-coordinate geometry to one Rb(2), two equivalent Rb(3), one P(1), and one Se(3) atom. The Se(2)-Se(3) bond length is 2.38 Å. In the third Se site, Se(3) is bonded in a distorted single-bond geometry to one Rb(1), two equivalent Rb(2), one Ge(1), and one Se(2) atom. In the fourth Se site, Se(4) is bonded to one Rb(1), one Rb(2), and two equivalent Ge(1) atoms to form distorted edge-sharing SeRb2Ge2 trigonal pyramids. In the fifth Se site, Se(5) is bonded in a 6-coordinate geometry to one Rb(2), two equivalent Rb(1), two equivalent Rb(3), and one Ge(1) atom. In the sixth Se site, Se(6) is bonded in a 4-coordinate geometry to one Rb(2), two equivalent Rb(3), and one P(1) atom. In the seventh Se site, Se(7) is bonded in a 5-coordinate geometry to one Rb(1), three equivalent Rb(2), and one P(1) atom.