TbVB4 crystallizes in the orthorhombic Pbam space group. Tb(1) is bonded in a 14-coordinate geometry to two equivalent B(4), four equivalent B(1), four equivalent B(2), and four equivalent B(3) atoms. V(1) is bonded in a 10-coordinate geometry to two equivalent B(1), two equivalent B(2), two equivalent B(3), and four equivalent B(4) atoms. There are four inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to four equivalent Tb(1), two equivalent V(1), one B(4), and two equivalent B(2) atoms. In the second B site, B(2) is bonded in a 9-coordinate geometry to four equivalent Tb(1), two equivalent V(1), one B(3), and two equivalent B(1) atoms. In the third B site, B(3) is bonded in a 9-coordinate geometry to four equivalent Tb(1), two equivalent V(1), one B(2), one B(3), and one B(4) atom. In the fourth B site, B(4) is bonded in a 9-coordinate geometry to two equivalent Tb(1), four equivalent V(1), one B(1), one B(3), and one B(4) atom.
TbVB4 crystallizes in the orthorhombic Pbam space group. Tb(1) is bonded in a 14-coordinate geometry to two equivalent B(4), four equivalent B(1), four equivalent B(2), and four equivalent B(3) atoms. Both Tb(1)-B(4) bond lengths are 2.63 Å. There are two shorter (2.67 Å) and two longer (2.77 Å) Tb(1)-B(1) bond lengths. There are two shorter (2.70 Å) and two longer (2.74 Å) Tb(1)-B(2) bond lengths. There are two shorter (2.71 Å) and two longer (2.75 Å) Tb(1)-B(3) bond lengths. V(1) is bonded in a 10-coordinate geometry to two equivalent B(1), two equivalent B(2), two equivalent B(3), and four equivalent B(4) atoms. Both V(1)-B(1) bond lengths are 2.32 Å. Both V(1)-B(2) bond lengths are 2.30 Å. Both V(1)-B(3) bond lengths are 2.31 Å. There are two shorter (2.29 Å) and two longer (2.30 Å) V(1)-B(4) bond lengths. There are four inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to four equivalent Tb(1), two equivalent V(1), one B(4), and two equivalent B(2) atoms. The B(1)-B(4) bond length is 1.77 Å. There is one shorter (1.84 Å) and one longer (1.86 Å) B(1)-B(2) bond length. In the second B site, B(2) is bonded in a 9-coordinate geometry to four equivalent Tb(1), two equivalent V(1), one B(3), and two equivalent B(1) atoms. The B(2)-B(3) bond length is 1.84 Å. In the third B site, B(3) is bonded in a 9-coordinate geometry to four equivalent Tb(1), two equivalent V(1), one B(2), one B(3), and one B(4) atom. The B(3)-B(3) bond length is 1.81 Å. The B(3)-B(4) bond length is 1.76 Å. In the fourth B site, B(4) is bonded in a 9-coordinate geometry to two equivalent Tb(1), four equivalent V(1), one B(1), one B(3), and one B(4) atom. The B(4)-B(4) bond length is 1.76 Å.