Tb4Ni11In20 crystallizes in the triclinic P1 space group. There are four inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 15-coordinate geometry to two equivalent Ni(5), two equivalent Ni(6), one In(1), one In(12), one In(20), one In(4), one In(9), two equivalent In(14), two equivalent In(15), and two equivalent In(8) atoms. In the second Tb site, Tb(2) is bonded in a 15-coordinate geometry to two equivalent Ni(1), two equivalent Ni(4), one In(11), one In(15), one In(19), one In(4), one In(7), two equivalent In(12), two equivalent In(13), and two equivalent In(18) atoms. In the third Tb site, Tb(3) is bonded in a 15-coordinate geometry to two equivalent Ni(3), two equivalent Ni(7), one In(11), one In(14), one In(2), one In(5), one In(6), two equivalent In(10), two equivalent In(17), and two equivalent In(20) atoms. In the fourth Tb site, Tb(4) is bonded in a 15-coordinate geometry to two equivalent Ni(8), two equivalent Ni(9), one In(1), one In(13), one In(16), one In(17), one In(5), two equivalent In(19), two equivalent In(2), and two equivalent In(3) atoms. There are eleven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 10-coordinate geometry to two equivalent Tb(2), one In(12), one In(13), one In(6), one In(9), two equivalent In(15), and two equivalent In(7) atoms. In the second Ni site, Ni(2) is bonded in a 10-coordinate geometry to one Ni(11), two equivalent Ni(10), one In(1), one In(11), one In(4), two equivalent In(18), and two equivalent In(8) atoms. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to two equivalent Tb(3), one In(1), one In(17), one In(20), two equivalent In(14), and two equivalent In(2) atoms. In the fourth Ni site, Ni(4) is bonded in a 9-coordinate geometry to two equivalent Tb(2), one In(13), one In(16), one In(18), two equivalent In(19), and two equivalent In(4) atoms. In the fifth Ni site, Ni(5) is bonded in a 9-coordinate geometry to two equivalent Tb(1), one In(15), one In(16), one In(8), two equivalent In(4), and two equivalent In(9) atoms. In the sixth Ni site, Ni(6) is bonded in a 9-coordinate geometry to two equivalent Tb(1), one In(11), one In(14), one In(15), two equivalent In(12), and two equivalent In(20) atoms. In the seventh Ni site, Ni(7) is bonded in a 9-coordinate geometry to two equivalent Tb(3), one In(10), one In(17), one In(7), two equivalent In(5), and two equivalent In(6) atoms. In the eighth Ni site, Ni(8) is bonded in a 9-coordinate geometry to two equivalent Tb(4), one In(19), one In(3), one In(7), two equivalent In(13), and two equivalent In(5) atoms. In the ninth Ni site, Ni(9) is bonded in a 10-coordinate geometry to two equivalent Tb(4), one In(19), one In(2), one In(6), one In(9), two equivalent In(16), and two equivalent In(17) atoms. In the tenth Ni site, Ni(10) is bonded to two equivalent Ni(11), two equivalent Ni(2), one In(10), one In(18), one In(3), one In(8), two equivalent In(1), and two equivalent In(11) atoms to form distorted face-sharing NiIn8Ni4 cuboctahedra. In the eleventh Ni site, Ni(11) is bonded in a 10-coordinate geometry to one Ni(2), two equivalent Ni(10), one In(1), one In(11), one In(5), two equivalent In(10), and two equivalent In(3) atoms. There are twenty inequivalent In sites. In the first In site, In(1) is bonded in a 3-coordinate geometry to one Tb(1), one Tb(4), one Ni(11), one Ni(2), one Ni(3), two equivalent Ni(10), and two equivalent In(14) atoms. In the second In site, In(2) is bonded in a 5-coordinate geometry to one Tb(3), two equivalent Tb(4), one Ni(9), two equivalent Ni(3), one In(14), and two equivalent In(17) atoms. In the third In site, In(3) is bonded in a 6-coordinate geometry to two equivalent Tb(4), one Ni(10), one Ni(8), and two equivalent Ni(11) atoms. In the fourth In site, In(4) is bonded in a 5-coordinate geometry to one Tb(1), one Tb(2), one Ni(2), two equivalent Ni(4), two equivalent Ni(5), one In(19), and one In(9) atom. In the fifth In site, In(5) is bonded in a 5-coordinate geometry to one Tb(3), one Tb(4), one Ni(11), two equivalent Ni(7), two equivalent Ni(8), one In(13), and one In(6) atom. In the sixth In site, In(6) is bonded in a 11-coordinate geometry to one Tb(3), one Ni(1), one Ni(9), two equivalent Ni(7), one In(5), one In(9), two equivalent In(17), and two equivalent In(7) atoms. In the seventh In site, In(7) is bonded in a 10-coordinate geometry to one Tb(2), one Ni(7), one Ni(8), two equivalent Ni(1), one In(15), two equivalent In(13), and two equivalent In(6) atoms. In the eighth In site, In(8) is bonded in a 6-coordinate geometry to two equivalent Tb(1), one Ni(10), one Ni(5), two equivalent Ni(2), and one In(14) atom. In the ninth In site, In(9) is bonded in a 11-coordinate geometry to one Tb(1), one Ni(1), one Ni(9), two equivalent Ni(5), one In(4), one In(6), two equivalent In(15), and two equivalent In(16) atoms. In the tenth In site, In(10) is bonded in a 6-coordinate geometry to two equivalent Tb(3), one Ni(10), one Ni(7), two equivalent Ni(11), and one In(20) atom. In the eleventh In site, In(11) is bonded in a 3-coordinate geometry to one Tb(2), one Tb(3), one Ni(11), one Ni(2), one Ni(6), two equivalent Ni(10), and two equivalent In(20) atoms. In the twelfth In site, In(12) is bonded in a 5-coordinate geometry to one Tb(1), two equivalent Tb(2), one Ni(1), two equivalent Ni(6), one In(20), and two equivalent In(15) atoms. In the thirteenth In site, In(13) is bonded in a 12-coordinate geometry to one Tb(4), two equivalent Tb(2), one Ni(1), one Ni(4), two equivalent Ni(8), one In(5), two equivalent In(19), and two equivalent In(7) atoms. In the fourteenth In site, In(14) is bonded in a 12-coordinate geometry to one Tb(3), two equivalent Tb(1), one Ni(6), two equivalent Ni(3), one In(2), one In(8), two equivalent In(1), and two equivalent In(20) atoms. In the fifteenth In site, In(15) is bonded in a 12-coordinate geometry to one Tb(2), two equivalent Tb(1), one Ni(5), one Ni(6), two equivalent Ni(1), one In(7), two equivalent In(12), and two equivalent In(9) atoms. In the sixteenth In site, In(16) is bonded in a 10-coordinate geometry to one Tb(4), one Ni(4), one Ni(5), two equivalent Ni(9), one In(17), two equivalent In(19), and two equivalent In(9) atoms. In the seventeenth In site, In(17) is bonded in a 12-coordinate geometry to one Tb(4), two equivalent Tb(3), one Ni(3), one Ni(7), two equivalent Ni(9), one In(16), two equivalent In(2), and two equivalent In(6) atoms. In the eighteenth In site, In(18) is bonded in a 6-coordinate geometry to two equivalent Tb(2), one Ni(10), one Ni(4), and two equivalent Ni(2) atoms. In the nineteenth In site, In(19) is bonded in a 12-coordinate geometry to one Tb(2), two equivalent Tb(4), one Ni(8), one Ni(9), two equivalent Ni(4), one In(4), two equivalent In(13), and two equivalent In(16) atoms. In the twentieth In site, In(20) is bonded in a 12-coordinate geometry to one Tb(1), two equivalent Tb(3), one Ni(3), two equivalent Ni(6), one In(10), one In(12), two equivalent In(11), and two equivalent In(14) atoms.
Tb4Ni11In20 crystallizes in the triclinic P1 space group. There are four inequivalent Tb sites. In the first Tb site, Tb(1) is bonded in a 15-coordinate geometry to two equivalent Ni(5), two equivalent Ni(6), one In(1), one In(12), one In(20), one In(4), one In(9), two equivalent In(14), two equivalent In(15), and two equivalent In(8) atoms. There is one shorter (3.12 Å) and one longer (3.16 Å) Tb(1)-Ni(5) bond length. There is one shorter (3.27 Å) and one longer (3.29 Å) Tb(1)-Ni(6) bond length. The Tb(1)-In(1) bond length is 3.66 Å. The Tb(1)-In(12) bond length is 3.30 Å. The Tb(1)-In(20) bond length is 3.34 Å. The Tb(1)-In(4) bond length is 3.42 Å. The Tb(1)-In(9) bond length is 3.24 Å. Both Tb(1)-In(14) bond lengths are 3.18 Å. There is one shorter (3.19 Å) and one longer (3.21 Å) Tb(1)-In(15) bond length. There is one shorter (3.14 Å) and one longer (3.15 Å) Tb(1)-In(8) bond length. In the second Tb site, Tb(2) is bonded in a 15-coordinate geometry to two equivalent Ni(1), two equivalent Ni(4), one In(11), one In(15), one In(19), one In(4), one In(7), two equivalent In(12), two equivalent In(13), and two equivalent In(18) atoms. There is one shorter (3.34 Å) and one longer (3.38 Å) Tb(2)-Ni(1) bond length. There is one shorter (3.17 Å) and one longer (3.18 Å) Tb(2)-Ni(4) bond length. The Tb(2)-In(11) bond length is 3.74 Å. The Tb(2)-In(15) bond length is 3.45 Å. The Tb(2)-In(19) bond length is 3.33 Å. The Tb(2)-In(4) bond length is 3.43 Å. The Tb(2)-In(7) bond length is 3.27 Å. Both Tb(2)-In(12) bond lengths are 3.14 Å. There is one shorter (3.18 Å) and one longer (3.20 Å) Tb(2)-In(13) bond length. Both Tb(2)-In(18) bond lengths are 3.15 Å. In the third Tb site, Tb(3) is bonded in a 15-coordinate geometry to two equivalent Ni(3), two equivalent Ni(7), one In(11), one In(14), one In(2), one In(5), one In(6), two equivalent In(10), two equivalent In(17), and two equivalent In(20) atoms. There is one shorter (3.27 Å) and one longer (3.29 Å) Tb(3)-Ni(3) bond length. There is one shorter (3.10 Å) and one longer (3.13 Å) Tb(3)-Ni(7) bond length. The Tb(3)-In(11) bond length is 3.71 Å. The Tb(3)-In(14) bond length is 3.34 Å. The Tb(3)-In(2) bond length is 3.30 Å. The Tb(3)-In(5) bond length is 3.39 Å. The Tb(3)-In(6) bond length is 3.24 Å. There is one shorter (3.15 Å) and one longer (3.16 Å) Tb(3)-In(10) bond length. There is one shorter (3.19 Å) and one longer (3.21 Å) Tb(3)-In(17) bond length. There is one shorter (3.18 Å) and one longer (3.19 Å) Tb(3)-In(20) bond length. In the fourth Tb site, Tb(4) is bonded in a 15-coordinate geometry to two equivalent Ni(8), two equivalent Ni(9), one In(1), one In(13), one In(16), one In(17), one In(5), two equivalent In(19), two equivalent In(2), and two equivalent In(3) atoms. There is one shorter (3.18 Å) and one longer (3.19 Å) Tb(4)-Ni(8) bond length. Both Tb(4)-Ni(9) bond lengths are 3.37 Å. The Tb(4)-In(1) bond length is 3.77 Å. The Tb(4)-In(13) bond length is 3.33 Å. The Tb(4)-In(16) bond length is 3.27 Å. The Tb(4)-In(17) bond length is 3.46 Å. The Tb(4)-In(5) bond length is 3.42 Å. Both Tb(4)-In(19) bond lengths are 3.18 Å. There is one shorter (3.15 Å) and one longer (3.16 Å) Tb(4)-In(2) bond length. There is one shorter (3.14 Å) and one longer (3.16 Å) Tb(4)-In(3) bond length. There are eleven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 10-coordinate geometry to two equivalent Tb(2), one In(12), one In(13), one In(6), one In(9), two equivalent In(15), and two equivalent In(7) atoms. The Ni(1)-In(12) bond length is 2.68 Å. The Ni(1)-In(13) bond length is 2.77 Å. The Ni(1)-In(6) bond length is 3.06 Å. The Ni(1)-In(9) bond length is 2.76 Å. There is one shorter (2.72 Å) and one longer (2.73 Å) Ni(1)-In(15) bond length. There is one shorter (2.65 Å) and one longer (2.66 Å) Ni(1)-In(7) bond length. In the second Ni site, Ni(2) is bonded in a 10-coordinate geometry to one Ni(11), two equivalent Ni(10), one In(1), one In(11), one In(4), two equivalent In(18), and two equivalent In(8) atoms. The Ni(2)-Ni(11) bond length is 2.87 Å. There is one shorter (2.59 Å) and one longer (2.60 Å) Ni(2)-Ni(10) bond length. The Ni(2)-In(1) bond length is 2.67 Å. The Ni(2)-In(11) bond length is 2.64 Å. The Ni(2)-In(4) bond length is 2.73 Å. There is one shorter (2.74 Å) and one longer (2.75 Å) Ni(2)-In(18) bond length. There is one shorter (2.72 Å) and one longer (2.73 Å) Ni(2)-In(8) bond length. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to two equivalent Tb(3), one In(1), one In(17), one In(20), two equivalent In(14), and two equivalent In(2) atoms. The Ni(3)-In(1) bond length is 2.65 Å. The Ni(3)-In(17) bond length is 2.72 Å. The Ni(3)-In(20) bond length is 2.65 Å. Both Ni(3)-In(14) bond lengths are 2.67 Å. Both Ni(3)-In(2) bond lengths are 2.65 Å. In the fourth Ni site, Ni(4) is bonded in a 9-coordinate geometry to two equivalent Tb(2), one In(13), one In(16), one In(18), two equivalent In(19), and two equivalent In(4) atoms. The Ni(4)-In(13) bond length is 2.69 Å. The Ni(4)-In(16) bond length is 2.69 Å. The Ni(4)-In(18) bond length is 2.70 Å. There is one shorter (2.74 Å) and one longer (2.75 Å) Ni(4)-In(19) bond length. There is one shorter (2.75 Å) and one longer (2.76 Å) Ni(4)-In(4) bond length. In the fifth Ni site, Ni(5) is bonded in a 9-coordinate geometry to two equivalent Tb(1), one In(15), one In(16), one In(8), two equivalent In(4), and two equivalent In(9) atoms. The Ni(5)-In(15) bond length is 2.72 Å. The Ni(5)-In(16) bond length is 2.63 Å. The Ni(5)-In(8) bond length is 2.66 Å. There is one shorter (2.75 Å) and one longer (2.78 Å) Ni(5)-In(4) bond length. Both Ni(5)-In(9) bond lengths are 2.74 Å. In the sixth Ni site, Ni(6) is bonded in a 9-coordinate geometry to two equivalent Tb(1), one In(11), one In(14), one In(15), two equivalent In(12), and two equivalent In(20) atoms. The Ni(6)-In(11) bond length is 2.67 Å. The Ni(6)-In(14) bond length is 2.65 Å. The Ni(6)-In(15) bond length is 2.71 Å. There is one shorter (2.65 Å) and one longer (2.66 Å) Ni(6)-In(12) bond length. Both Ni(6)-In(20) bond lengths are 2.68 Å. In the seventh Ni site, Ni(7) is bonded in a 9-coordinate geometry to two equivalent Tb(3), one In(10), one In(17), one In(7), two equivalent In(5), and two equivalent In(6) atoms. The Ni(7)-In(10) bond length is 2.66 Å. The Ni(7)-In(17) bond length is 2.72 Å. The Ni(7)-In(7) bond length is 2.64 Å. There is one shorter (2.76 Å) and one longer (2.77 Å) Ni(7)-In(5) bond length. There is one shorter (2.75 Å) and one longer (2.76 Å) Ni(7)-In(6) bond length. In the eighth Ni site, Ni(8) is bonded in a 9-coordinate geometry to two equivalent Tb(4), one In(19), one In(3), one In(7), two equivalent In(13), and two equivalent In(5) atoms. The Ni(8)-In(19) bond length is 2.71 Å. The Ni(8)-In(3) bond length is 2.72 Å. The Ni(8)-In(7) bond length is 2.70 Å. There is one shorter (2.75 Å) and one longer (2.76 Å) Ni(8)-In(13) bond length. There is one shorter (2.74 Å) and one longer (2.75 Å) Ni(8)-In(5) bond length. In the ninth Ni site, Ni(9) is bonded in a 10-coordinate geometry to two equivalent Tb(4), one In(19), one In(2), one In(6), one In(9), two equivalent In(16), and two equivalent In(17) atoms. The Ni(9)-In(19) bond length is 2.79 Å. The Ni(9)-In(2) bond length is 2.66 Å. The Ni(9)-In(6) bond length is 2.77 Å. The Ni(9)-In(9) bond length is 3.08 Å. There is one shorter (2.66 Å) and one longer (2.67 Å) Ni(9)-In(16) bond length. There is one shorter (2.71 Å) and one longer (2.73 Å) Ni(9)-In(17) bond length. In the tenth Ni site, Ni(10) is bonded to two equivalent Ni(11), two equivalent Ni(2), one In(10), one In(18), one In(3), one In(8), two equivalent In(1), and two equivalent In(11) atoms to form distorted face-sharing NiIn8Ni4 cuboctahedra. Both Ni(10)-Ni(11) bond lengths are 2.59 Å. The Ni(10)-In(10) bond length is 2.65 Å. The Ni(10)-In(18) bond length is 2.70 Å. The Ni(10)-In(3) bond length is 2.72 Å. The Ni(10)-In(8) bond length is 2.67 Å. There is one shorter (3.13 Å) and one longer (3.14 Å) Ni(10)-In(1) bond length. There is one shorter (3.07 Å) and one longer (3.09 Å) Ni(10)-In(11) bond length. In the eleventh Ni site, Ni(11) is bonded in a 10-coordinate geometry to one Ni(2), two equivalent Ni(10), one In(1), one In(11), one In(5), two equivalent In(10), and two equivalent In(3) atoms. The Ni(11)-In(1) bond length is 2.63 Å. The Ni(11)-In(11) bond length is 2.68 Å. The Ni(11)-In(5) bond length is 2.74 Å. There is one shorter (2.73 Å) and one longer (2.75 Å) Ni(11)-In(10) bond length. There is one shorter (2.73 Å) and one longer (2.75 Å) Ni(11)-In(3) bond length. There are twenty inequivalent In sites. In the first In site, In(1) is bonded in a 3-coordinate geometry to one Tb(1), one Tb(4), one Ni(11), one Ni(2), one Ni(3), two equivalent Ni(10), and two equivalent In(14) atoms. There is one shorter (3.29 Å) and one longer (3.32 Å) In(1)-In(14) bond length. In the second In site, In(2) is bonded in a 5-coordinate geometry to one Tb(3), two equivalent Tb(4), one Ni(9), two equivalent Ni(3), one In(14), and two equivalent In(17) atoms. The In(2)-In(14) bond length is 2.95 Å. Both In(2)-In(17) bond lengths are 3.09 Å. In the third In site, In(3) is bonded in a 6-coordinate geometry to two equivalent Tb(4), one Ni(10), one Ni(8), and two equivalent Ni(11) atoms. In the fourth In site, In(4) is bonded in a 5-coordinate geometry to one Tb(1), one Tb(2), one Ni(2), two equivalent Ni(4), two equivalent Ni(5), one In(19), and one In(9) atom. The In(4)-In(19) bond length is 3.12 Å. The In(4)-In(9) bond length is 3.14 Å. In the fifth In site, In(5) is bonded in a 5-coordinate geometry to one Tb(3), one Tb(4), one Ni(11), two equivalent Ni(7), two equivalent Ni(8), one In(13), and one In(6) atom. The In(5)-In(13) bond length is 3.13 Å. The In(5)-In(6) bond length is 3.16 Å. In the sixth In site, In(6) is bonded in a 11-coordinate geometry to one Tb(3), one Ni(1), one Ni(9), two equivalent Ni(7), one In(5), one In(9), two equivalent In(17), and two equivalent In(7) atoms. The In(6)-In(9) bond length is 2.94 Å. There is one shorter (3.07 Å) and one longer (3.09 Å) In(6)-In(17) bond length. There is one shorter (2.98 Å) and one longer (2.99 Å) In(6)-In(7) bond length. In the seventh In site, In(7) is bonded in a 10-coordinate geometry to one Tb(2), one Ni(7), one Ni(8), two equivalent Ni(1), one In(15), two equivalent In(13), and two equivalent In(6) atoms. The In(7)-In(15) bond length is 3.09 Å. There is one shorter (3.04 Å) and one longer (3.06 Å) In(7)-In(13) bond length. In the eighth In site, In(8) is bonded in a 6-coordinate geometry to two equivalent Tb(1), one Ni(10), one Ni(5), two equivalent Ni(2), and one In(14) atom. The In(8)-In(14) bond length is 3.02 Å. In the ninth In site, In(9) is bonded in a 11-coordinate geometry to one Tb(1), one Ni(1), one Ni(9), two equivalent Ni(5), one In(4), one In(6), two equivalent In(15), and two equivalent In(16) atoms. There is one shorter (3.06 Å) and one longer (3.08 Å) In(9)-In(15) bond length. There is one shorter (3.00 Å) and one longer (3.01 Å) In(9)-In(16) bond length. In the tenth In site, In(10) is bonded in a 6-coordinate geometry to two equivalent Tb(3), one Ni(10), one Ni(7), two equivalent Ni(11), and one In(20) atom. The In(10)-In(20) bond length is 3.00 Å. In the eleventh In site, In(11) is bonded in a 3-coordinate geometry to one Tb(2), one Tb(3), one Ni(11), one Ni(2), one Ni(6), two equivalent Ni(10), and two equivalent In(20) atoms. There is one shorter (3.31 Å) and one longer (3.35 Å) In(11)-In(20) bond length. In the twelfth In site, In(12) is bonded in a 5-coordinate geometry to one Tb(1), two equivalent Tb(2), one Ni(1), two equivalent Ni(6), one In(20), and two equivalent In(15) atoms. The In(12)-In(20) bond length is 2.95 Å. There is one shorter (3.08 Å) and one longer (3.11 Å) In(12)-In(15) bond length. In the thirteenth In site, In(13) is bonded in a 12-coordinate geometry to one Tb(4), two equivalent Tb(2), one Ni(1), one Ni(4), two equivalent Ni(8), one In(5), two equivalent In(19), and two equivalent In(7) atoms. Both In(13)-In(19) bond lengths are 3.11 Å. In the fourteenth In site, In(14) is bonded in a 12-coordinate geometry to one Tb(3), two equivalent Tb(1), one Ni(6), two equivalent Ni(3), one In(2), one In(8), two equivalent In(1), and two equivalent In(20) atoms. There is one shorter (3.06 Å) and one longer (3.07 Å) In(14)-In(20) bond length. In the fifteenth In site, In(15) is bonded in a 12-coordinate geometry to one Tb(2), two equivalent Tb(1), one Ni(5), one Ni(6), two equivalent Ni(1), one In(7), two equivalent In(12), and two equivalent In(9) atoms. In the sixteenth In site, In(16) is bonded in a 10-coordinate geometry to one Tb(4), one Ni(4), one Ni(5), two equivalent Ni(9), one In(17), two equivalent In(19), and two equivalent In(9) atoms. The In(16)-In(17) bond length is 3.09 Å. There is one shorter (3.05 Å) and one longer (3.06 Å) In(16)-In(19) bond length. In the seventeenth In site, In(17) is bonded in a 12-coordinate geometry to one Tb(4), two equivalent Tb(3), one Ni(3), one Ni(7), two equivalent Ni(9), one In(16), two equivalent In(2), and two equivalent In(6) atoms. In the eighteenth In site, In(18) is bonded in a 6-coordinate geometry to two equivalent Tb(2), one Ni(10), one Ni(4), and two equivalent Ni(2) atoms. In the nineteenth In site, In(19) is bonded in a 12-coordinate geometry to one Tb(2), two equivalent Tb(4), one Ni(8), one Ni(9), two equivalent Ni(4), one In(4), two equivalent In(13), and two equivalent In(16) atoms. In the twentieth In site, In(20) is bonded in a 12-coordinate geometry to one Tb(1), two equivalent Tb(3), one Ni(3), two equivalent Ni(6), one In(10), one In(12), two equivalent In(11), and two equivalent In(14) atoms.