NdNi4B crystallizes in the orthorhombic Imma space group. There are three inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a 6-coordinate geometry to one Ni(3), two equivalent Ni(5), and three equivalent Ni(6) atoms. In the second Nd site, Nd(2) is bonded in a 18-coordinate geometry to one Ni(5), two equivalent Ni(3), four equivalent Ni(7), eight equivalent Ni(1), one B(2), and two equivalent B(1) atoms. In the third Nd site, Nd(3) is bonded in a 17-coordinate geometry to four equivalent Ni(1), four equivalent Ni(2), four equivalent Ni(4), two equivalent B(2), and three equivalent B(3) atoms. There are seven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 2-coordinate geometry to one Nd(3), two equivalent Nd(2), one Ni(3), one Ni(5), one B(1), and one B(2) atom. In the second Ni site, Ni(2) is bonded in a distorted L-shaped geometry to two equivalent Nd(3), one Ni(5), one Ni(6), one B(2), and one B(3) atom. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to one Nd(1), two equivalent Nd(2), two equivalent Ni(5), two equivalent Ni(7), and four equivalent Ni(1) atoms. In the fourth Ni site, Ni(4) is bonded in a distorted L-shaped geometry to two equivalent Nd(3), two equivalent Ni(6), and two equivalent B(3) atoms. In the fifth Ni site, Ni(5) is bonded in a 12-coordinate geometry to one Nd(2), two equivalent Nd(1), one Ni(6), two equivalent Ni(2), two equivalent Ni(3), and four equivalent Ni(1) atoms. In the sixth Ni site, Ni(6) is bonded in a 9-coordinate geometry to three equivalent Nd(1), one Ni(5), two equivalent Ni(2), and four equivalent Ni(4) atoms. In the seventh Ni site, Ni(7) is bonded in a distorted linear geometry to four equivalent Nd(2), two equivalent Ni(3), and two equivalent B(1) atoms. There are three inequivalent B sites. In the first B site, B(3) is bonded in a 6-coordinate geometry to three equivalent Nd(3), two equivalent Ni(2), and four equivalent Ni(4) atoms. In the second B site, B(1) is bonded in a 6-coordinate geometry to two equivalent Nd(2), two equivalent Ni(7), and four equivalent Ni(1) atoms. In the third B site, B(2) is bonded in a 6-coordinate geometry to one Nd(2), two equivalent Nd(3), two equivalent Ni(2), and four equivalent Ni(1) atoms.
NdNi4B crystallizes in the orthorhombic Imma space group. There are three inequivalent Nd sites. In the first Nd site, Nd(1) is bonded in a 6-coordinate geometry to one Ni(3), two equivalent Ni(5), and three equivalent Ni(6) atoms. The Nd(1)-Ni(3) bond length is 2.77 Å. Both Nd(1)-Ni(5) bond lengths are 2.92 Å. There is one shorter (2.83 Å) and two longer (2.88 Å) Nd(1)-Ni(6) bond lengths. In the second Nd site, Nd(2) is bonded in a 18-coordinate geometry to one Ni(5), two equivalent Ni(3), four equivalent Ni(7), eight equivalent Ni(1), one B(2), and two equivalent B(1) atoms. The Nd(2)-Ni(5) bond length is 2.71 Å. Both Nd(2)-Ni(3) bond lengths are 2.89 Å. All Nd(2)-Ni(7) bond lengths are 3.07 Å. There are four shorter (3.01 Å) and four longer (3.09 Å) Nd(2)-Ni(1) bond lengths. The Nd(2)-B(2) bond length is 3.11 Å. Both Nd(2)-B(1) bond lengths are 2.91 Å. In the third Nd site, Nd(3) is bonded in a 17-coordinate geometry to four equivalent Ni(1), four equivalent Ni(2), four equivalent Ni(4), two equivalent B(2), and three equivalent B(3) atoms. All Nd(3)-Ni(1) bond lengths are 2.87 Å. All Nd(3)-Ni(2) bond lengths are 2.90 Å. All Nd(3)-Ni(4) bond lengths are 2.94 Å. Both Nd(3)-B(2) bond lengths are 2.91 Å. There are two shorter (2.93 Å) and one longer (2.99 Å) Nd(3)-B(3) bond length. There are seven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 2-coordinate geometry to one Nd(3), two equivalent Nd(2), one Ni(3), one Ni(5), one B(1), and one B(2) atom. The Ni(1)-Ni(3) bond length is 2.49 Å. The Ni(1)-Ni(5) bond length is 2.60 Å. The Ni(1)-B(1) bond length is 2.07 Å. The Ni(1)-B(2) bond length is 2.01 Å. In the second Ni site, Ni(2) is bonded in a distorted L-shaped geometry to two equivalent Nd(3), one Ni(5), one Ni(6), one B(2), and one B(3) atom. The Ni(2)-Ni(5) bond length is 2.49 Å. The Ni(2)-Ni(6) bond length is 2.51 Å. The Ni(2)-B(2) bond length is 2.09 Å. The Ni(2)-B(3) bond length is 2.01 Å. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to one Nd(1), two equivalent Nd(2), two equivalent Ni(5), two equivalent Ni(7), and four equivalent Ni(1) atoms. Both Ni(3)-Ni(5) bond lengths are 2.83 Å. Both Ni(3)-Ni(7) bond lengths are 2.40 Å. In the fourth Ni site, Ni(4) is bonded in a distorted L-shaped geometry to two equivalent Nd(3), two equivalent Ni(6), and two equivalent B(3) atoms. Both Ni(4)-Ni(6) bond lengths are 2.50 Å. Both Ni(4)-B(3) bond lengths are 2.05 Å. In the fifth Ni site, Ni(5) is bonded in a 12-coordinate geometry to one Nd(2), two equivalent Nd(1), one Ni(6), two equivalent Ni(2), two equivalent Ni(3), and four equivalent Ni(1) atoms. The Ni(5)-Ni(6) bond length is 2.87 Å. In the sixth Ni site, Ni(6) is bonded in a 9-coordinate geometry to three equivalent Nd(1), one Ni(5), two equivalent Ni(2), and four equivalent Ni(4) atoms. In the seventh Ni site, Ni(7) is bonded in a distorted linear geometry to four equivalent Nd(2), two equivalent Ni(3), and two equivalent B(1) atoms. Both Ni(7)-B(1) bond lengths are 2.11 Å. There are three inequivalent B sites. In the first B site, B(3) is bonded in a 6-coordinate geometry to three equivalent Nd(3), two equivalent Ni(2), and four equivalent Ni(4) atoms. In the second B site, B(1) is bonded in a 6-coordinate geometry to two equivalent Nd(2), two equivalent Ni(7), and four equivalent Ni(1) atoms. In the third B site, B(2) is bonded in a 6-coordinate geometry to one Nd(2), two equivalent Nd(3), two equivalent Ni(2), and four equivalent Ni(1) atoms.