K2Sn5Cl12 crystallizes in the monoclinic Pm space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to one Cl(12), one Cl(14), two equivalent Cl(1), and two equivalent Cl(4) atoms to form distorted KCl6 pentagonal pyramids that share corners with two equivalent Sn(1)Cl4 trigonal pyramids. In the second K site, K(2) is bonded in a 6-coordinate geometry to one Cl(15), one Cl(6), two equivalent Cl(2), and two equivalent Cl(3) atoms. In the third K site, K(3) is bonded in a 7-coordinate geometry to one Cl(13), one Cl(17), one Cl(6), two equivalent Cl(3), and two equivalent Cl(8) atoms. In the fourth K site, K(4) is bonded in a 9-coordinate geometry to one Cl(14), one Cl(18), one Cl(7), two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(8) atoms. There are seven inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one Cl(11), one Cl(13), and two equivalent Cl(4) atoms to form SnCl4 trigonal pyramids that share corners with two equivalent K(1)Cl6 pentagonal pyramids. In the second Sn site, Sn(2) is bonded in a trigonal pyramidal geometry to one Cl(16), one Cl(7), and two equivalent Cl(2) atoms. In the third Sn site, Sn(3) is bonded to one Cl(10), one Cl(18), and two equivalent Cl(5) atoms to form corner-sharing SnCl4 trigonal pyramids. In the fourth Sn site, Sn(4) is bonded to one Cl(17), one Cl(9), and two equivalent Cl(5) atoms to form corner-sharing SnCl4 trigonal pyramids. In the fifth Sn site, Sn(5) is bonded in a 4-coordinate geometry to one Cl(1), one Cl(12), one Cl(5), and one Cl(6) atom. In the sixth Sn site, Sn(6) is bonded in a 3-coordinate geometry to one Cl(14), one Cl(2), and one Cl(8) atom. In the seventh Sn site, Sn(7) is bonded in a distorted trigonal non-coplanar geometry to one Cl(15), one Cl(3), and one Cl(4) atom. There are eighteen inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to one K(1), one K(4), and one Sn(5) atom. In the second Cl site, Cl(2) is bonded in a distorted trigonal non-coplanar geometry to one K(2), one Sn(2), and one Sn(6) atom. In the third Cl site, Cl(3) is bonded in a 4-coordinate geometry to one K(2), one K(3), one K(4), and one Sn(7) atom. In the fourth Cl site, Cl(4) is bonded in a trigonal non-coplanar geometry to one K(1), one Sn(1), and one Sn(7) atom. In the fifth Cl site, Cl(5) is bonded in a trigonal planar geometry to one Sn(3), one Sn(4), and one Sn(5) atom. In the sixth Cl site, Cl(6) is bonded in a distorted tetrahedral geometry to one K(2), one K(3), and two equivalent Sn(5) atoms. In the seventh Cl site, Cl(7) is bonded in a distorted bent 120 degrees geometry to one K(4) and one Sn(2) atom. In the eighth Cl site, Cl(8) is bonded in a 3-coordinate geometry to one K(3), one K(4), and one Sn(6) atom. In the ninth Cl site, Cl(9) is bonded in a single-bond geometry to one Sn(4) atom. In the tenth Cl site, Cl(10) is bonded in a distorted single-bond geometry to one Sn(3) atom. In the eleventh Cl site, Cl(11) is bonded in a single-bond geometry to one Sn(1) atom. In the twelfth Cl site, Cl(12) is bonded in a distorted T-shaped geometry to one K(1) and two equivalent Sn(5) atoms. In the thirteenth Cl site, Cl(13) is bonded in a bent 150 degrees geometry to one K(3) and one Sn(1) atom. In the fourteenth Cl site, Cl(14) is bonded in a 4-coordinate geometry to one K(1), one K(4), and two equivalent Sn(6) atoms. In the fifteenth Cl site, Cl(15) is bonded in a trigonal non-coplanar geometry to one K(2) and two equivalent Sn(7) atoms. In the sixteenth Cl site, Cl(16) is bonded in a single-bond geometry to one Sn(2) atom. In the seventeenth Cl site, Cl(17) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Sn(4) atom. In the eighteenth Cl site, Cl(18) is bonded in a bent 120 degrees geometry to one K(4) and one Sn(3) atom.
K2Sn5Cl12 crystallizes in the monoclinic Pm space group. There are four inequivalent K sites. In the first K site, K(1) is bonded to one Cl(12), one Cl(14), two equivalent Cl(1), and two equivalent Cl(4) atoms to form distorted KCl6 pentagonal pyramids that share corners with two equivalent Sn(1)Cl4 trigonal pyramids. The K(1)-Cl(12) bond length is 3.04 Å. The K(1)-Cl(14) bond length is 3.40 Å. Both K(1)-Cl(1) bond lengths are 3.29 Å. Both K(1)-Cl(4) bond lengths are 3.26 Å. In the second K site, K(2) is bonded in a 6-coordinate geometry to one Cl(15), one Cl(6), two equivalent Cl(2), and two equivalent Cl(3) atoms. The K(2)-Cl(15) bond length is 3.19 Å. The K(2)-Cl(6) bond length is 3.26 Å. Both K(2)-Cl(2) bond lengths are 3.16 Å. Both K(2)-Cl(3) bond lengths are 3.67 Å. In the third K site, K(3) is bonded in a 7-coordinate geometry to one Cl(13), one Cl(17), one Cl(6), two equivalent Cl(3), and two equivalent Cl(8) atoms. The K(3)-Cl(13) bond length is 3.13 Å. The K(3)-Cl(17) bond length is 3.39 Å. The K(3)-Cl(6) bond length is 3.51 Å. Both K(3)-Cl(3) bond lengths are 3.27 Å. Both K(3)-Cl(8) bond lengths are 3.12 Å. In the fourth K site, K(4) is bonded in a 9-coordinate geometry to one Cl(14), one Cl(18), one Cl(7), two equivalent Cl(1), two equivalent Cl(3), and two equivalent Cl(8) atoms. The K(4)-Cl(14) bond length is 3.64 Å. The K(4)-Cl(18) bond length is 3.11 Å. The K(4)-Cl(7) bond length is 3.19 Å. Both K(4)-Cl(1) bond lengths are 3.32 Å. Both K(4)-Cl(3) bond lengths are 3.40 Å. Both K(4)-Cl(8) bond lengths are 3.40 Å. There are seven inequivalent Sn sites. In the first Sn site, Sn(1) is bonded to one Cl(11), one Cl(13), and two equivalent Cl(4) atoms to form SnCl4 trigonal pyramids that share corners with two equivalent K(1)Cl6 pentagonal pyramids. The Sn(1)-Cl(11) bond length is 2.60 Å. The Sn(1)-Cl(13) bond length is 2.47 Å. Both Sn(1)-Cl(4) bond lengths are 2.89 Å. In the second Sn site, Sn(2) is bonded in a trigonal pyramidal geometry to one Cl(16), one Cl(7), and two equivalent Cl(2) atoms. The Sn(2)-Cl(16) bond length is 2.60 Å. The Sn(2)-Cl(7) bond length is 2.48 Å. Both Sn(2)-Cl(2) bond lengths are 2.98 Å. In the third Sn site, Sn(3) is bonded to one Cl(10), one Cl(18), and two equivalent Cl(5) atoms to form corner-sharing SnCl4 trigonal pyramids. The Sn(3)-Cl(10) bond length is 2.56 Å. The Sn(3)-Cl(18) bond length is 2.60 Å. Both Sn(3)-Cl(5) bond lengths are 2.88 Å. In the fourth Sn site, Sn(4) is bonded to one Cl(17), one Cl(9), and two equivalent Cl(5) atoms to form corner-sharing SnCl4 trigonal pyramids. The Sn(4)-Cl(17) bond length is 2.54 Å. The Sn(4)-Cl(9) bond length is 2.54 Å. Both Sn(4)-Cl(5) bond lengths are 2.95 Å. In the fifth Sn site, Sn(5) is bonded in a 4-coordinate geometry to one Cl(1), one Cl(12), one Cl(5), and one Cl(6) atom. The Sn(5)-Cl(1) bond length is 2.50 Å. The Sn(5)-Cl(12) bond length is 3.02 Å. The Sn(5)-Cl(5) bond length is 2.86 Å. The Sn(5)-Cl(6) bond length is 2.87 Å. In the sixth Sn site, Sn(6) is bonded in a 3-coordinate geometry to one Cl(14), one Cl(2), and one Cl(8) atom. The Sn(6)-Cl(14) bond length is 2.70 Å. The Sn(6)-Cl(2) bond length is 2.75 Å. The Sn(6)-Cl(8) bond length is 2.47 Å. In the seventh Sn site, Sn(7) is bonded in a distorted trigonal non-coplanar geometry to one Cl(15), one Cl(3), and one Cl(4) atom. The Sn(7)-Cl(15) bond length is 2.78 Å. The Sn(7)-Cl(3) bond length is 2.50 Å. The Sn(7)-Cl(4) bond length is 2.80 Å. There are eighteen inequivalent Cl sites. In the first Cl site, Cl(1) is bonded in a 3-coordinate geometry to one K(1), one K(4), and one Sn(5) atom. In the second Cl site, Cl(2) is bonded in a distorted trigonal non-coplanar geometry to one K(2), one Sn(2), and one Sn(6) atom. In the third Cl site, Cl(3) is bonded in a 4-coordinate geometry to one K(2), one K(3), one K(4), and one Sn(7) atom. In the fourth Cl site, Cl(4) is bonded in a trigonal non-coplanar geometry to one K(1), one Sn(1), and one Sn(7) atom. In the fifth Cl site, Cl(5) is bonded in a trigonal planar geometry to one Sn(3), one Sn(4), and one Sn(5) atom. In the sixth Cl site, Cl(6) is bonded in a distorted tetrahedral geometry to one K(2), one K(3), and two equivalent Sn(5) atoms. In the seventh Cl site, Cl(7) is bonded in a distorted bent 120 degrees geometry to one K(4) and one Sn(2) atom. In the eighth Cl site, Cl(8) is bonded in a 3-coordinate geometry to one K(3), one K(4), and one Sn(6) atom. In the ninth Cl site, Cl(9) is bonded in a single-bond geometry to one Sn(4) atom. In the tenth Cl site, Cl(10) is bonded in a distorted single-bond geometry to one Sn(3) atom. In the eleventh Cl site, Cl(11) is bonded in a single-bond geometry to one Sn(1) atom. In the twelfth Cl site, Cl(12) is bonded in a distorted T-shaped geometry to one K(1) and two equivalent Sn(5) atoms. In the thirteenth Cl site, Cl(13) is bonded in a bent 150 degrees geometry to one K(3) and one Sn(1) atom. In the fourteenth Cl site, Cl(14) is bonded in a 4-coordinate geometry to one K(1), one K(4), and two equivalent Sn(6) atoms. In the fifteenth Cl site, Cl(15) is bonded in a trigonal non-coplanar geometry to one K(2) and two equivalent Sn(7) atoms. In the sixteenth Cl site, Cl(16) is bonded in a single-bond geometry to one Sn(2) atom. In the seventeenth Cl site, Cl(17) is bonded in a distorted bent 120 degrees geometry to one K(3) and one Sn(4) atom. In the eighteenth Cl site, Cl(18) is bonded in a bent 120 degrees geometry to one K(4) and one Sn(3) atom.