Rb4(BSe)9 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one B(8), one Se(3), one Se(6), one Se(8), one Se(9), two equivalent Se(2), and two equivalent Se(7) atoms. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one Se(1), one Se(3), one Se(4), one Se(5), one Se(9), and two equivalent Se(8) atoms. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Se(1), one Se(4), one Se(6), one Se(8), two equivalent Se(7), and two equivalent Se(9) atoms. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one Se(2), one Se(4), one Se(7), one Se(8), one Se(9), and two equivalent Se(5) atoms. There are nine inequivalent B sites. In the first B site, B(1) is bonded in a distorted single-bond geometry to one B(2), one B(3), one B(4), one B(5), one B(6), and one Se(1) atom. In the second B site, B(2) is bonded in a 6-coordinate geometry to one B(1), one B(3), one B(4), one B(5), one B(6), and one Se(2) atom. In the third B site, B(3) is bonded in a distorted single-bond geometry to one B(1), one B(2), one B(4), one B(5), one B(6), and one Se(3) atom. In the fourth B site, B(4) is bonded in a distorted single-bond geometry to one B(1), one B(2), one B(3), one B(5), one B(6), and one Se(4) atom. In the fifth B site, B(5) is bonded in a 6-coordinate geometry to one B(1), one B(2), one B(3), one B(4), one B(6), and one Se(5) atom. In the sixth B site, B(6) is bonded in a distorted single-bond geometry to one B(1), one B(2), one B(3), one B(4), one B(5), and one Se(6) atom. In the seventh B site, B(7) is bonded in a trigonal planar geometry to one Se(1), one Se(2), and one Se(7) atom. In the eighth B site, B(8) is bonded in a trigonal planar geometry to one Rb(1), one Se(3), one Se(4), and one Se(8) atom. In the ninth B site, B(9) is bonded in a trigonal planar geometry to one Se(5), one Se(6), and one Se(9) atom. There are nine inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted water-like geometry to one Rb(2), one Rb(3), one B(1), and one B(7) atom. In the second Se site, Se(2) is bonded in a distorted water-like geometry to one Rb(4), two equivalent Rb(1), one B(2), and one B(7) atom. In the third Se site, Se(3) is bonded in a distorted L-shaped geometry to one Rb(1), one Rb(2), one B(3), and one B(8) atom. In the fourth Se site, Se(4) is bonded in a distorted water-like geometry to one Rb(2), one Rb(3), one Rb(4), one B(4), and one B(8) atom. In the fifth Se site, Se(5) is bonded in a distorted water-like geometry to one Rb(2), two equivalent Rb(4), one B(5), and one B(9) atom. In the sixth Se site, Se(6) is bonded in a distorted L-shaped geometry to one Rb(1), one Rb(3), one B(6), and one B(9) atom. In the seventh Se site, Se(7) is bonded in a distorted single-bond geometry to one Rb(4), two equivalent Rb(1), two equivalent Rb(3), and one B(7) atom. In the eighth Se site, Se(8) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), one Rb(4), two equivalent Rb(2), and one B(8) atom. In the ninth Se site, Se(9) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), one Rb(4), two equivalent Rb(3), and one B(9) atom.
Rb4(BSe)9 crystallizes in the triclinic P-1 space group. There are four inequivalent Rb sites. In the first Rb site, Rb(1) is bonded in a 9-coordinate geometry to one B(8), one Se(3), one Se(6), one Se(8), one Se(9), two equivalent Se(2), and two equivalent Se(7) atoms. The Rb(1)-B(8) bond length is 3.66 Å. The Rb(1)-Se(3) bond length is 3.64 Å. The Rb(1)-Se(6) bond length is 3.52 Å. The Rb(1)-Se(8) bond length is 3.79 Å. The Rb(1)-Se(9) bond length is 3.94 Å. There is one shorter (3.63 Å) and one longer (3.79 Å) Rb(1)-Se(2) bond length. There is one shorter (3.54 Å) and one longer (3.63 Å) Rb(1)-Se(7) bond length. In the second Rb site, Rb(2) is bonded in a 7-coordinate geometry to one Se(1), one Se(3), one Se(4), one Se(5), one Se(9), and two equivalent Se(8) atoms. The Rb(2)-Se(1) bond length is 3.55 Å. The Rb(2)-Se(3) bond length is 3.50 Å. The Rb(2)-Se(4) bond length is 3.63 Å. The Rb(2)-Se(5) bond length is 3.62 Å. The Rb(2)-Se(9) bond length is 3.49 Å. There is one shorter (3.55 Å) and one longer (3.58 Å) Rb(2)-Se(8) bond length. In the third Rb site, Rb(3) is bonded in a 8-coordinate geometry to one Se(1), one Se(4), one Se(6), one Se(8), two equivalent Se(7), and two equivalent Se(9) atoms. The Rb(3)-Se(1) bond length is 3.80 Å. The Rb(3)-Se(4) bond length is 3.76 Å. The Rb(3)-Se(6) bond length is 3.60 Å. The Rb(3)-Se(8) bond length is 3.44 Å. There is one shorter (3.69 Å) and one longer (3.83 Å) Rb(3)-Se(7) bond length. There is one shorter (3.64 Å) and one longer (3.80 Å) Rb(3)-Se(9) bond length. In the fourth Rb site, Rb(4) is bonded in a 7-coordinate geometry to one Se(2), one Se(4), one Se(7), one Se(8), one Se(9), and two equivalent Se(5) atoms. The Rb(4)-Se(2) bond length is 3.64 Å. The Rb(4)-Se(4) bond length is 3.86 Å. The Rb(4)-Se(7) bond length is 3.76 Å. The Rb(4)-Se(8) bond length is 3.70 Å. The Rb(4)-Se(9) bond length is 3.70 Å. There is one shorter (3.76 Å) and one longer (3.78 Å) Rb(4)-Se(5) bond length. There are nine inequivalent B sites. In the first B site, B(1) is bonded in a distorted single-bond geometry to one B(2), one B(3), one B(4), one B(5), one B(6), and one Se(1) atom. The B(1)-B(2) bond length is 1.77 Å. The B(1)-B(3) bond length is 1.77 Å. The B(1)-B(4) bond length is 1.78 Å. The B(1)-B(5) bond length is 1.78 Å. The B(1)-B(6) bond length is 1.77 Å. The B(1)-Se(1) bond length is 2.00 Å. In the second B site, B(2) is bonded in a 6-coordinate geometry to one B(1), one B(3), one B(4), one B(5), one B(6), and one Se(2) atom. The B(2)-B(3) bond length is 1.78 Å. The B(2)-B(4) bond length is 1.79 Å. The B(2)-B(5) bond length is 1.79 Å. The B(2)-B(6) bond length is 1.78 Å. The B(2)-Se(2) bond length is 2.01 Å. In the third B site, B(3) is bonded in a distorted single-bond geometry to one B(1), one B(2), one B(4), one B(5), one B(6), and one Se(3) atom. The B(3)-B(4) bond length is 1.78 Å. The B(3)-B(5) bond length is 1.78 Å. The B(3)-B(6) bond length is 1.77 Å. The B(3)-Se(3) bond length is 2.00 Å. In the fourth B site, B(4) is bonded in a distorted single-bond geometry to one B(1), one B(2), one B(3), one B(5), one B(6), and one Se(4) atom. The B(4)-B(5) bond length is 1.79 Å. The B(4)-B(6) bond length is 1.77 Å. The B(4)-Se(4) bond length is 2.00 Å. In the fifth B site, B(5) is bonded in a 6-coordinate geometry to one B(1), one B(2), one B(3), one B(4), one B(6), and one Se(5) atom. The B(5)-B(6) bond length is 1.78 Å. The B(5)-Se(5) bond length is 2.01 Å. In the sixth B site, B(6) is bonded in a distorted single-bond geometry to one B(1), one B(2), one B(3), one B(4), one B(5), and one Se(6) atom. The B(6)-Se(6) bond length is 1.99 Å. In the seventh B site, B(7) is bonded in a trigonal planar geometry to one Se(1), one Se(2), and one Se(7) atom. The B(7)-Se(1) bond length is 1.97 Å. The B(7)-Se(2) bond length is 1.99 Å. The B(7)-Se(7) bond length is 1.90 Å. In the eighth B site, B(8) is bonded in a trigonal planar geometry to one Rb(1), one Se(3), one Se(4), and one Se(8) atom. The B(8)-Se(3) bond length is 1.97 Å. The B(8)-Se(4) bond length is 1.99 Å. The B(8)-Se(8) bond length is 1.90 Å. In the ninth B site, B(9) is bonded in a trigonal planar geometry to one Se(5), one Se(6), and one Se(9) atom. The B(9)-Se(5) bond length is 1.99 Å. The B(9)-Se(6) bond length is 1.98 Å. The B(9)-Se(9) bond length is 1.90 Å. There are nine inequivalent Se sites. In the first Se site, Se(1) is bonded in a distorted water-like geometry to one Rb(2), one Rb(3), one B(1), and one B(7) atom. In the second Se site, Se(2) is bonded in a distorted water-like geometry to one Rb(4), two equivalent Rb(1), one B(2), and one B(7) atom. In the third Se site, Se(3) is bonded in a distorted L-shaped geometry to one Rb(1), one Rb(2), one B(3), and one B(8) atom. In the fourth Se site, Se(4) is bonded in a distorted water-like geometry to one Rb(2), one Rb(3), one Rb(4), one B(4), and one B(8) atom. In the fifth Se site, Se(5) is bonded in a distorted water-like geometry to one Rb(2), two equivalent Rb(4), one B(5), and one B(9) atom. In the sixth Se site, Se(6) is bonded in a distorted L-shaped geometry to one Rb(1), one Rb(3), one B(6), and one B(9) atom. In the seventh Se site, Se(7) is bonded in a distorted single-bond geometry to one Rb(4), two equivalent Rb(1), two equivalent Rb(3), and one B(7) atom. In the eighth Se site, Se(8) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(3), one Rb(4), two equivalent Rb(2), and one B(8) atom. In the ninth Se site, Se(9) is bonded in a distorted single-bond geometry to one Rb(1), one Rb(2), one Rb(4), two equivalent Rb(3), and one B(9) atom.