Tb(Ni2B)6 crystallizes in the orthorhombic Cmc2_1 space group. Tb(1) is bonded in a 24-coordinate geometry to one Ni(3), one Ni(5), two equivalent Ni(4), two equivalent Ni(7), four equivalent Ni(1), four equivalent Ni(2), four equivalent Ni(6), one B(3), one B(4), two equivalent B(1), and two equivalent B(2) atoms. There are seven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to two equivalent Tb(1), one B(1), one B(4), and two equivalent B(2) atoms. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to two equivalent Tb(1), one B(2), one B(3), and two equivalent B(1) atoms. In the third Ni site, Ni(3) is bonded in a 3-coordinate geometry to one Tb(1), one B(4), and two equivalent B(2) atoms. In the fourth Ni site, Ni(4) is bonded in a 3-coordinate geometry to one Tb(1), one B(1), one B(2), and one B(3) atom. In the fifth Ni site, Ni(5) is bonded in a 3-coordinate geometry to one Tb(1), one B(3), and two equivalent B(1) atoms. In the sixth Ni site, Ni(6) is bonded in a 3-coordinate geometry to two equivalent Tb(1), one B(1), one B(2), and one B(4) atom. In the seventh Ni site, Ni(7) is bonded to one Tb(1), one B(1), one B(2), one B(3), and one B(4) atom to form distorted face-sharing NiTbB4 tetrahedra. There are four inequivalent B sites. In the first B site, B(1) is bonded in a 7-coordinate geometry to one Tb(1), one Ni(1), one Ni(4), one Ni(5), one Ni(6), one Ni(7), and two equivalent Ni(2) atoms. In the second B site, B(2) is bonded in a 7-coordinate geometry to one Tb(1), one Ni(2), one Ni(3), one Ni(4), one Ni(6), one Ni(7), and two equivalent Ni(1) atoms. In the third B site, B(3) is bonded in a 7-coordinate geometry to one Tb(1), one Ni(5), two equivalent Ni(2), two equivalent Ni(4), and two equivalent Ni(7) atoms. In the fourth B site, B(4) is bonded in a 8-coordinate geometry to one Tb(1), one Ni(3), two equivalent Ni(1), two equivalent Ni(6), and two equivalent Ni(7) atoms.
Tb(Ni2B)6 crystallizes in the orthorhombic Cmc2_1 space group. Tb(1) is bonded in a 24-coordinate geometry to one Ni(3), one Ni(5), two equivalent Ni(4), two equivalent Ni(7), four equivalent Ni(1), four equivalent Ni(2), four equivalent Ni(6), one B(3), one B(4), two equivalent B(1), and two equivalent B(2) atoms. The Tb(1)-Ni(3) bond length is 3.06 Å. The Tb(1)-Ni(5) bond length is 3.04 Å. Both Tb(1)-Ni(4) bond lengths are 3.01 Å. Both Tb(1)-Ni(7) bond lengths are 3.11 Å. There are two shorter (3.19 Å) and two longer (3.28 Å) Tb(1)-Ni(1) bond lengths. There are two shorter (3.17 Å) and two longer (3.38 Å) Tb(1)-Ni(2) bond lengths. There are two shorter (3.13 Å) and two longer (3.38 Å) Tb(1)-Ni(6) bond lengths. The Tb(1)-B(3) bond length is 3.08 Å. The Tb(1)-B(4) bond length is 2.99 Å. Both Tb(1)-B(1) bond lengths are 3.29 Å. Both Tb(1)-B(2) bond lengths are 3.11 Å. There are seven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to two equivalent Tb(1), one B(1), one B(4), and two equivalent B(2) atoms. The Ni(1)-B(1) bond length is 2.04 Å. The Ni(1)-B(4) bond length is 2.06 Å. There is one shorter (2.02 Å) and one longer (2.10 Å) Ni(1)-B(2) bond length. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to two equivalent Tb(1), one B(2), one B(3), and two equivalent B(1) atoms. The Ni(2)-B(2) bond length is 2.02 Å. The Ni(2)-B(3) bond length is 2.09 Å. There is one shorter (2.03 Å) and one longer (2.07 Å) Ni(2)-B(1) bond length. In the third Ni site, Ni(3) is bonded in a 3-coordinate geometry to one Tb(1), one B(4), and two equivalent B(2) atoms. The Ni(3)-B(4) bond length is 2.17 Å. Both Ni(3)-B(2) bond lengths are 2.10 Å. In the fourth Ni site, Ni(4) is bonded in a 3-coordinate geometry to one Tb(1), one B(1), one B(2), and one B(3) atom. The Ni(4)-B(1) bond length is 2.14 Å. The Ni(4)-B(2) bond length is 2.06 Å. The Ni(4)-B(3) bond length is 2.11 Å. In the fifth Ni site, Ni(5) is bonded in a 3-coordinate geometry to one Tb(1), one B(3), and two equivalent B(1) atoms. The Ni(5)-B(3) bond length is 2.08 Å. Both Ni(5)-B(1) bond lengths are 1.99 Å. In the sixth Ni site, Ni(6) is bonded in a 3-coordinate geometry to two equivalent Tb(1), one B(1), one B(2), and one B(4) atom. The Ni(6)-B(1) bond length is 2.09 Å. The Ni(6)-B(2) bond length is 2.04 Å. The Ni(6)-B(4) bond length is 2.03 Å. In the seventh Ni site, Ni(7) is bonded to one Tb(1), one B(1), one B(2), one B(3), and one B(4) atom to form distorted face-sharing NiTbB4 tetrahedra. The Ni(7)-B(1) bond length is 1.98 Å. The Ni(7)-B(2) bond length is 2.09 Å. The Ni(7)-B(3) bond length is 2.05 Å. The Ni(7)-B(4) bond length is 2.07 Å. There are four inequivalent B sites. In the first B site, B(1) is bonded in a 7-coordinate geometry to one Tb(1), one Ni(1), one Ni(4), one Ni(5), one Ni(6), one Ni(7), and two equivalent Ni(2) atoms. In the second B site, B(2) is bonded in a 7-coordinate geometry to one Tb(1), one Ni(2), one Ni(3), one Ni(4), one Ni(6), one Ni(7), and two equivalent Ni(1) atoms. In the third B site, B(3) is bonded in a 7-coordinate geometry to one Tb(1), one Ni(5), two equivalent Ni(2), two equivalent Ni(4), and two equivalent Ni(7) atoms. In the fourth B site, B(4) is bonded in a 8-coordinate geometry to one Tb(1), one Ni(3), two equivalent Ni(1), two equivalent Ni(6), and two equivalent Ni(7) atoms.