Cs4Hg2Sn21 crystallizes in the orthorhombic Ama2 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 20-coordinate geometry to one Sn(11), one Sn(12), one Sn(6), one Sn(9), two equivalent Sn(1), two equivalent Sn(10), two equivalent Sn(2), two equivalent Sn(3), two equivalent Sn(4), two equivalent Sn(5), two equivalent Sn(7), and two equivalent Sn(8) atoms. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Sn(11), two equivalent Sn(12), two equivalent Sn(6), and two equivalent Sn(9) atoms. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to two equivalent Sn(10), two equivalent Sn(5), two equivalent Sn(7), and two equivalent Sn(8) atoms. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to two equivalent Sn(10), two equivalent Sn(5), two equivalent Sn(7), and two equivalent Sn(8) atoms. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted tetrahedral geometry to two equivalent Sn(10) and two equivalent Sn(7) atoms. In the second Hg site, Hg(2) is bonded in a distorted tetrahedral geometry to one Sn(12), one Sn(9), and two equivalent Sn(8) atoms. There are thirteen inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(1), one Sn(5), one Sn(6), and one Sn(7) atom. In the second Sn site, Sn(2) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(10), one Sn(2), one Sn(8), and one Sn(9) atom. In the third Sn site, Sn(3) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(11), one Sn(4), one Sn(7), and one Sn(8) atom. In the fourth Sn site, Sn(4) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(10), one Sn(12), one Sn(3), and one Sn(5) atom. In the fifth Sn site, Sn(5) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Sn(1), one Sn(13), one Sn(4), and one Sn(8) atom. In the sixth Sn site, Sn(6) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Sn(12), one Sn(13), and two equivalent Sn(1) atoms. In the seventh Sn site, Sn(7) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Hg(1), one Sn(1), one Sn(3), and one Sn(7) atom. In the eighth Sn site, Sn(8) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Hg(2), one Sn(2), one Sn(3), and one Sn(5) atom. In the ninth Sn site, Sn(9) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Hg(2), one Sn(11), and two equivalent Sn(2) atoms. In the tenth Sn site, Sn(10) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Hg(1), one Sn(10), one Sn(2), and one Sn(4) atom. In the eleventh Sn site, Sn(11) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Sn(13), one Sn(9), and two equivalent Sn(3) atoms. In the twelfth Sn site, Sn(12) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Hg(2), one Sn(6), and two equivalent Sn(4) atoms. In the thirteenth Sn site, Sn(13) is bonded in a distorted tetrahedral geometry to one Sn(11), one Sn(6), and two equivalent Sn(5) atoms.
Cs4Hg2Sn21 crystallizes in the orthorhombic Ama2 space group. There are four inequivalent Cs sites. In the first Cs site, Cs(1) is bonded in a 20-coordinate geometry to one Sn(11), one Sn(12), one Sn(6), one Sn(9), two equivalent Sn(1), two equivalent Sn(10), two equivalent Sn(2), two equivalent Sn(3), two equivalent Sn(4), two equivalent Sn(5), two equivalent Sn(7), and two equivalent Sn(8) atoms. The Cs(1)-Sn(11) bond length is 4.04 Å. The Cs(1)-Sn(12) bond length is 4.17 Å. The Cs(1)-Sn(6) bond length is 4.07 Å. The Cs(1)-Sn(9) bond length is 4.13 Å. Both Cs(1)-Sn(1) bond lengths are 3.95 Å. Both Cs(1)-Sn(10) bond lengths are 4.11 Å. Both Cs(1)-Sn(2) bond lengths are 3.90 Å. Both Cs(1)-Sn(3) bond lengths are 3.93 Å. Both Cs(1)-Sn(4) bond lengths are 3.93 Å. Both Cs(1)-Sn(5) bond lengths are 4.05 Å. Both Cs(1)-Sn(7) bond lengths are 4.16 Å. Both Cs(1)-Sn(8) bond lengths are 4.15 Å. In the second Cs site, Cs(2) is bonded in a 8-coordinate geometry to two equivalent Sn(11), two equivalent Sn(12), two equivalent Sn(6), and two equivalent Sn(9) atoms. Both Cs(2)-Sn(11) bond lengths are 4.16 Å. Both Cs(2)-Sn(12) bond lengths are 4.14 Å. Both Cs(2)-Sn(6) bond lengths are 4.24 Å. Both Cs(2)-Sn(9) bond lengths are 4.07 Å. In the third Cs site, Cs(3) is bonded in a 8-coordinate geometry to two equivalent Sn(10), two equivalent Sn(5), two equivalent Sn(7), and two equivalent Sn(8) atoms. Both Cs(3)-Sn(10) bond lengths are 4.05 Å. Both Cs(3)-Sn(5) bond lengths are 4.25 Å. Both Cs(3)-Sn(7) bond lengths are 4.12 Å. Both Cs(3)-Sn(8) bond lengths are 4.16 Å. In the fourth Cs site, Cs(4) is bonded in a 8-coordinate geometry to two equivalent Sn(10), two equivalent Sn(5), two equivalent Sn(7), and two equivalent Sn(8) atoms. Both Cs(4)-Sn(10) bond lengths are 4.05 Å. Both Cs(4)-Sn(5) bond lengths are 4.24 Å. Both Cs(4)-Sn(7) bond lengths are 4.12 Å. Both Cs(4)-Sn(8) bond lengths are 4.16 Å. There are two inequivalent Hg sites. In the first Hg site, Hg(1) is bonded in a distorted tetrahedral geometry to two equivalent Sn(10) and two equivalent Sn(7) atoms. Both Hg(1)-Sn(10) bond lengths are 2.83 Å. Both Hg(1)-Sn(7) bond lengths are 2.83 Å. In the second Hg site, Hg(2) is bonded in a distorted tetrahedral geometry to one Sn(12), one Sn(9), and two equivalent Sn(8) atoms. The Hg(2)-Sn(12) bond length is 2.81 Å. The Hg(2)-Sn(9) bond length is 2.81 Å. Both Hg(2)-Sn(8) bond lengths are 2.80 Å. There are thirteen inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(1), one Sn(5), one Sn(6), and one Sn(7) atom. The Sn(1)-Sn(1) bond length is 2.83 Å. The Sn(1)-Sn(5) bond length is 2.87 Å. The Sn(1)-Sn(6) bond length is 2.87 Å. The Sn(1)-Sn(7) bond length is 2.88 Å. In the second Sn site, Sn(2) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(10), one Sn(2), one Sn(8), and one Sn(9) atom. The Sn(2)-Sn(10) bond length is 2.88 Å. The Sn(2)-Sn(2) bond length is 2.88 Å. The Sn(2)-Sn(8) bond length is 2.88 Å. The Sn(2)-Sn(9) bond length is 2.88 Å. In the third Sn site, Sn(3) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(11), one Sn(4), one Sn(7), and one Sn(8) atom. The Sn(3)-Sn(11) bond length is 2.87 Å. The Sn(3)-Sn(4) bond length is 2.85 Å. The Sn(3)-Sn(7) bond length is 2.87 Å. The Sn(3)-Sn(8) bond length is 2.88 Å. In the fourth Sn site, Sn(4) is bonded in a 5-coordinate geometry to one Cs(1), one Sn(10), one Sn(12), one Sn(3), and one Sn(5) atom. The Sn(4)-Sn(10) bond length is 2.88 Å. The Sn(4)-Sn(12) bond length is 2.88 Å. The Sn(4)-Sn(5) bond length is 2.87 Å. In the fifth Sn site, Sn(5) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Sn(1), one Sn(13), one Sn(4), and one Sn(8) atom. The Sn(5)-Sn(13) bond length is 2.91 Å. The Sn(5)-Sn(8) bond length is 2.94 Å. In the sixth Sn site, Sn(6) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Sn(12), one Sn(13), and two equivalent Sn(1) atoms. The Sn(6)-Sn(12) bond length is 2.92 Å. The Sn(6)-Sn(13) bond length is 2.91 Å. In the seventh Sn site, Sn(7) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Hg(1), one Sn(1), one Sn(3), and one Sn(7) atom. The Sn(7)-Sn(7) bond length is 2.92 Å. In the eighth Sn site, Sn(8) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Hg(2), one Sn(2), one Sn(3), and one Sn(5) atom. In the ninth Sn site, Sn(9) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Hg(2), one Sn(11), and two equivalent Sn(2) atoms. The Sn(9)-Sn(11) bond length is 2.94 Å. In the tenth Sn site, Sn(10) is bonded in a 7-coordinate geometry to one Cs(1), one Cs(3), one Cs(4), one Hg(1), one Sn(10), one Sn(2), and one Sn(4) atom. The Sn(10)-Sn(10) bond length is 2.94 Å. In the eleventh Sn site, Sn(11) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Sn(13), one Sn(9), and two equivalent Sn(3) atoms. The Sn(11)-Sn(13) bond length is 2.91 Å. In the twelfth Sn site, Sn(12) is bonded in a 7-coordinate geometry to one Cs(1), two equivalent Cs(2), one Hg(2), one Sn(6), and two equivalent Sn(4) atoms. In the thirteenth Sn site, Sn(13) is bonded in a distorted tetrahedral geometry to one Sn(11), one Sn(6), and two equivalent Sn(5) atoms.