GdNiB4 crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 20-coordinate geometry to four equivalent Ni(1), eight equivalent B(1), and eight equivalent B(2) atoms. In the second Gd site, Gd(2) is bonded in a 20-coordinate geometry to four equivalent Ni(1), eight equivalent B(1), and eight equivalent B(2) atoms. Ni(1) is bonded in a 6-coordinate geometry to two equivalent Gd(1), two equivalent Gd(2), two equivalent B(1), and four equivalent B(2) atoms. There are two inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to two equivalent Gd(1), two equivalent Gd(2), one Ni(1), two equivalent B(1), and two equivalent B(2) atoms. In the second B site, B(2) is bonded in a 9-coordinate geometry to two equivalent Gd(1), two equivalent Gd(2), two equivalent Ni(1), one B(2), and two equivalent B(1) atoms.
GdNiB4 crystallizes in the tetragonal I4/mmm space group. There are two inequivalent Gd sites. In the first Gd site, Gd(1) is bonded in a 20-coordinate geometry to four equivalent Ni(1), eight equivalent B(1), and eight equivalent B(2) atoms. All Gd(1)-Ni(1) bond lengths are 3.07 Å. All Gd(1)-B(1) bond lengths are 2.84 Å. There are four shorter (2.80 Å) and four longer (2.88 Å) Gd(1)-B(2) bond lengths. In the second Gd site, Gd(2) is bonded in a 20-coordinate geometry to four equivalent Ni(1), eight equivalent B(1), and eight equivalent B(2) atoms. All Gd(2)-Ni(1) bond lengths are 2.96 Å. All Gd(2)-B(1) bond lengths are 2.86 Å. All Gd(2)-B(2) bond lengths are 2.81 Å. Ni(1) is bonded in a 6-coordinate geometry to two equivalent Gd(1), two equivalent Gd(2), two equivalent B(1), and four equivalent B(2) atoms. Both Ni(1)-B(1) bond lengths are 2.09 Å. All Ni(1)-B(2) bond lengths are 2.20 Å. There are two inequivalent B sites. In the first B site, B(1) is bonded in a 9-coordinate geometry to two equivalent Gd(1), two equivalent Gd(2), one Ni(1), two equivalent B(1), and two equivalent B(2) atoms. There is one shorter (1.69 Å) and one longer (1.76 Å) B(1)-B(1) bond length. Both B(1)-B(2) bond lengths are 1.75 Å. In the second B site, B(2) is bonded in a 9-coordinate geometry to two equivalent Gd(1), two equivalent Gd(2), two equivalent Ni(1), one B(2), and two equivalent B(1) atoms. The B(2)-B(2) bond length is 1.70 Å.