Y4ZrNi25 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in a 18-coordinate geometry to one Ni(2), one Ni(5), two equivalent Ni(1), two equivalent Ni(4), four equivalent Ni(10), four equivalent Ni(7), and four equivalent Ni(9) atoms. In the second Y site, Y(2) is bonded in a 18-coordinate geometry to one Ni(4), two equivalent Ni(2), three equivalent Ni(3), four equivalent Ni(10), four equivalent Ni(11), and four equivalent Ni(8) atoms. Zr(1) is bonded in a 18-coordinate geometry to two equivalent Ni(1), four equivalent Ni(5), four equivalent Ni(6), and eight equivalent Ni(9) atoms. There are eleven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 9-coordinate geometry to two equivalent Y(1), one Zr(1), two equivalent Ni(5), two equivalent Ni(7), and four equivalent Ni(9) atoms. In the second Ni site, Ni(2) is bonded in a 9-coordinate geometry to one Y(1), two equivalent Y(2), two equivalent Ni(8), and four equivalent Ni(10) atoms. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to three equivalent Y(2), two equivalent Ni(8), and four equivalent Ni(11) atoms. In the fourth Ni site, Ni(4) is bonded in a 9-coordinate geometry to one Y(2), two equivalent Y(1), two equivalent Ni(7), and four equivalent Ni(10) atoms. In the fifth Ni site, Ni(5) is bonded in a 12-coordinate geometry to one Y(1), two equivalent Zr(1), one Ni(5), two equivalent Ni(1), two equivalent Ni(6), and four equivalent Ni(9) atoms. In the sixth Ni site, Ni(6) is bonded to four equivalent Zr(1), four equivalent Ni(5), and four equivalent Ni(9) atoms to form NiZr4Ni8 cuboctahedra that share corners with four equivalent Ni(7)Y4Ni8 cuboctahedra, corners with four equivalent Ni(6)Zr4Ni8 cuboctahedra, corners with eight equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, edges with two equivalent Ni(6)Zr4Ni8 cuboctahedra, edges with eight equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, faces with two equivalent Ni(6)Zr4Ni8 cuboctahedra, and faces with eight equivalent Ni(9)Y2Zr2Ni8 cuboctahedra. In the seventh Ni site, Ni(7) is bonded to four equivalent Y(1), two equivalent Ni(1), two equivalent Ni(10), two equivalent Ni(4), and two equivalent Ni(9) atoms to form NiY4Ni8 cuboctahedra that share corners with two equivalent Ni(8)Y4Ni8 cuboctahedra, corners with two equivalent Ni(6)Zr4Ni8 cuboctahedra, corners with four equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, corners with four equivalent Ni(10)Y4Ni8 cuboctahedra, corners with four equivalent Ni(7)Y4Ni8 cuboctahedra, edges with two equivalent Ni(7)Y4Ni8 cuboctahedra, edges with four equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, edges with four equivalent Ni(10)Y4Ni8 cuboctahedra, faces with two equivalent Ni(7)Y4Ni8 cuboctahedra, faces with four equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, and faces with four equivalent Ni(10)Y4Ni8 cuboctahedra. In the eighth Ni site, Ni(8) is bonded to four equivalent Y(2), two equivalent Ni(10), two equivalent Ni(11), two equivalent Ni(2), and two equivalent Ni(3) atoms to form a mixture of edge, face, and corner-sharing NiY4Ni8 cuboctahedra. In the ninth Ni site, Ni(9) is bonded to two equivalent Y(1), two equivalent Zr(1), one Ni(6), one Ni(7), two equivalent Ni(1), two equivalent Ni(5), and two equivalent Ni(9) atoms to form NiY2Zr2Ni8 cuboctahedra that share corners with two equivalent Ni(7)Y4Ni8 cuboctahedra, corners with two equivalent Ni(6)Zr4Ni8 cuboctahedra, corners with five equivalent Ni(10)Y4Ni8 cuboctahedra, corners with seven equivalent Ni(9)Y2Zr2Ni8 cuboctahedra,  an edgeedge with one Ni(10)Y4Ni8 cuboctahedra, edges with two equivalent Ni(7)Y4Ni8 cuboctahedra, edges with two equivalent Ni(6)Zr4Ni8 cuboctahedra, edges with five equivalent Ni(9)Y2Zr2Ni8 cuboctahedra,  a faceface with one Ni(10)Y4Ni8 cuboctahedra, faces with two equivalent Ni(7)Y4Ni8 cuboctahedra, faces with two equivalent Ni(6)Zr4Ni8 cuboctahedra, and faces with five equivalent Ni(9)Y2Zr2Ni8 cuboctahedra. In the tenth Ni site, Ni(10) is bonded to two equivalent Y(1), two equivalent Y(2), one Ni(7), one Ni(8), two equivalent Ni(10), two equivalent Ni(2), and two equivalent Ni(4) atoms to form NiY4Ni8 cuboctahedra that share corners with two equivalent Ni(10)Y4Ni8 cuboctahedra, corners with two equivalent Ni(7)Y4Ni8 cuboctahedra, corners with two equivalent Ni(8)Y4Ni8 cuboctahedra, corners with five equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, corners with five equivalent Ni(11)Y4Ni8 cuboctahedra,  an edgeedge with one Ni(9)Y2Zr2Ni8 cuboctahedra,  an edgeedge with one Ni(11)Y4Ni8 cuboctahedra, edges with two equivalent Ni(7)Y4Ni8 cuboctahedra, edges with two equivalent Ni(8)Y4Ni8 cuboctahedra, edges with four equivalent Ni(10)Y4Ni8 cuboctahedra,  a faceface with one Ni(9)Y2Zr2Ni8 cuboctahedra,  a faceface with one Ni(11)Y4Ni8 cuboctahedra, faces with two equivalent Ni(7)Y4Ni8 cuboctahedra, faces with two equivalent Ni(8)Y4Ni8 cuboctahedra, and faces with four equivalent Ni(10)Y4Ni8 cuboctahedra. In the eleventh Ni site, Ni(11) is bonded to four equivalent Y(2), two equivalent Ni(11), two equivalent Ni(8), and four equivalent Ni(3) atoms to form a mixture of edge, face, and corner-sharing NiY4Ni8 cuboctahedra.
Y4ZrNi25 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Y sites. In the first Y site, Y(1) is bonded in a 18-coordinate geometry to one Ni(2), one Ni(5), two equivalent Ni(1), two equivalent Ni(4), four equivalent Ni(10), four equivalent Ni(7), and four equivalent Ni(9) atoms. The Y(1)-Ni(2) bond length is 2.80 Å. The Y(1)-Ni(5) bond length is 2.85 Å. Both Y(1)-Ni(1) bond lengths are 2.83 Å. Both Y(1)-Ni(4) bond lengths are 2.81 Å. All Y(1)-Ni(10) bond lengths are 3.12 Å. All Y(1)-Ni(7) bond lengths are 3.13 Å. All Y(1)-Ni(9) bond lengths are 3.15 Å. In the second Y site, Y(2) is bonded in a 18-coordinate geometry to one Ni(4), two equivalent Ni(2), three equivalent Ni(3), four equivalent Ni(10), four equivalent Ni(11), and four equivalent Ni(8) atoms. The Y(2)-Ni(4) bond length is 2.81 Å. Both Y(2)-Ni(2) bond lengths are 2.81 Å. All Y(2)-Ni(3) bond lengths are 2.81 Å. All Y(2)-Ni(10) bond lengths are 3.12 Å. All Y(2)-Ni(11) bond lengths are 3.13 Å. All Y(2)-Ni(8) bond lengths are 3.13 Å. Zr(1) is bonded in a 18-coordinate geometry to two equivalent Ni(1), four equivalent Ni(5), four equivalent Ni(6), and eight equivalent Ni(9) atoms. Both Zr(1)-Ni(1) bond lengths are 2.77 Å. All Zr(1)-Ni(5) bond lengths are 2.79 Å. All Zr(1)-Ni(6) bond lengths are 3.13 Å. All Zr(1)-Ni(9) bond lengths are 3.10 Å. There are eleven inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 9-coordinate geometry to two equivalent Y(1), one Zr(1), two equivalent Ni(5), two equivalent Ni(7), and four equivalent Ni(9) atoms. Both Ni(1)-Ni(5) bond lengths are 2.81 Å. Both Ni(1)-Ni(7) bond lengths are 2.44 Å. All Ni(1)-Ni(9) bond lengths are 2.40 Å. In the second Ni site, Ni(2) is bonded in a 9-coordinate geometry to one Y(1), two equivalent Y(2), two equivalent Ni(8), and four equivalent Ni(10) atoms. Both Ni(2)-Ni(8) bond lengths are 2.41 Å. All Ni(2)-Ni(10) bond lengths are 2.42 Å. In the third Ni site, Ni(3) is bonded in a 9-coordinate geometry to three equivalent Y(2), two equivalent Ni(8), and four equivalent Ni(11) atoms. Both Ni(3)-Ni(8) bond lengths are 2.41 Å. All Ni(3)-Ni(11) bond lengths are 2.42 Å. In the fourth Ni site, Ni(4) is bonded in a 9-coordinate geometry to one Y(2), two equivalent Y(1), two equivalent Ni(7), and four equivalent Ni(10) atoms. Both Ni(4)-Ni(7) bond lengths are 2.41 Å. All Ni(4)-Ni(10) bond lengths are 2.41 Å. In the fifth Ni site, Ni(5) is bonded in a 12-coordinate geometry to one Y(1), two equivalent Zr(1), one Ni(5), two equivalent Ni(1), two equivalent Ni(6), and four equivalent Ni(9) atoms. The Ni(5)-Ni(5) bond length is 2.72 Å. Both Ni(5)-Ni(6) bond lengths are 2.39 Å. All Ni(5)-Ni(9) bond lengths are 2.43 Å. In the sixth Ni site, Ni(6) is bonded to four equivalent Zr(1), four equivalent Ni(5), and four equivalent Ni(9) atoms to form NiZr4Ni8 cuboctahedra that share corners with four equivalent Ni(7)Y4Ni8 cuboctahedra, corners with four equivalent Ni(6)Zr4Ni8 cuboctahedra, corners with eight equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, edges with two equivalent Ni(6)Zr4Ni8 cuboctahedra, edges with eight equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, faces with two equivalent Ni(6)Zr4Ni8 cuboctahedra, and faces with eight equivalent Ni(9)Y2Zr2Ni8 cuboctahedra. All Ni(6)-Ni(9) bond lengths are 2.42 Å. In the seventh Ni site, Ni(7) is bonded to four equivalent Y(1), two equivalent Ni(1), two equivalent Ni(10), two equivalent Ni(4), and two equivalent Ni(9) atoms to form NiY4Ni8 cuboctahedra that share corners with two equivalent Ni(8)Y4Ni8 cuboctahedra, corners with two equivalent Ni(6)Zr4Ni8 cuboctahedra, corners with four equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, corners with four equivalent Ni(10)Y4Ni8 cuboctahedra, corners with four equivalent Ni(7)Y4Ni8 cuboctahedra, edges with two equivalent Ni(7)Y4Ni8 cuboctahedra, edges with four equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, edges with four equivalent Ni(10)Y4Ni8 cuboctahedra, faces with two equivalent Ni(7)Y4Ni8 cuboctahedra, faces with four equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, and faces with four equivalent Ni(10)Y4Ni8 cuboctahedra. Both Ni(7)-Ni(10) bond lengths are 2.43 Å. Both Ni(7)-Ni(9) bond lengths are 2.44 Å. In the eighth Ni site, Ni(8) is bonded to four equivalent Y(2), two equivalent Ni(10), two equivalent Ni(11), two equivalent Ni(2), and two equivalent Ni(3) atoms to form a mixture of edge, face, and corner-sharing NiY4Ni8 cuboctahedra. Both Ni(8)-Ni(10) bond lengths are 2.43 Å. Both Ni(8)-Ni(11) bond lengths are 2.43 Å. In the ninth Ni site, Ni(9) is bonded to two equivalent Y(1), two equivalent Zr(1), one Ni(6), one Ni(7), two equivalent Ni(1), two equivalent Ni(5), and two equivalent Ni(9) atoms to form NiY2Zr2Ni8 cuboctahedra that share corners with two equivalent Ni(7)Y4Ni8 cuboctahedra, corners with two equivalent Ni(6)Zr4Ni8 cuboctahedra, corners with five equivalent Ni(10)Y4Ni8 cuboctahedra, corners with seven equivalent Ni(9)Y2Zr2Ni8 cuboctahedra,  an edgeedge with one Ni(10)Y4Ni8 cuboctahedra, edges with two equivalent Ni(7)Y4Ni8 cuboctahedra, edges with two equivalent Ni(6)Zr4Ni8 cuboctahedra, edges with five equivalent Ni(9)Y2Zr2Ni8 cuboctahedra,  a faceface with one Ni(10)Y4Ni8 cuboctahedra, faces with two equivalent Ni(7)Y4Ni8 cuboctahedra, faces with two equivalent Ni(6)Zr4Ni8 cuboctahedra, and faces with five equivalent Ni(9)Y2Zr2Ni8 cuboctahedra. There is one shorter (2.41 Å) and one longer (2.47 Å) Ni(9)-Ni(9) bond length. In the tenth Ni site, Ni(10) is bonded to two equivalent Y(1), two equivalent Y(2), one Ni(7), one Ni(8), two equivalent Ni(10), two equivalent Ni(2), and two equivalent Ni(4) atoms to form NiY4Ni8 cuboctahedra that share corners with two equivalent Ni(10)Y4Ni8 cuboctahedra, corners with two equivalent Ni(7)Y4Ni8 cuboctahedra, corners with two equivalent Ni(8)Y4Ni8 cuboctahedra, corners with five equivalent Ni(9)Y2Zr2Ni8 cuboctahedra, corners with five equivalent Ni(11)Y4Ni8 cuboctahedra,  an edgeedge with one Ni(9)Y2Zr2Ni8 cuboctahedra,  an edgeedge with one Ni(11)Y4Ni8 cuboctahedra, edges with two equivalent Ni(7)Y4Ni8 cuboctahedra, edges with two equivalent Ni(8)Y4Ni8 cuboctahedra, edges with four equivalent Ni(10)Y4Ni8 cuboctahedra,  a faceface with one Ni(9)Y2Zr2Ni8 cuboctahedra,  a faceface with one Ni(11)Y4Ni8 cuboctahedra, faces with two equivalent Ni(7)Y4Ni8 cuboctahedra, faces with two equivalent Ni(8)Y4Ni8 cuboctahedra, and faces with four equivalent Ni(10)Y4Ni8 cuboctahedra. Both Ni(10)-Ni(10) bond lengths are 2.44 Å. In the eleventh Ni site, Ni(11) is bonded to four equivalent Y(2), two equivalent Ni(11), two equivalent Ni(8), and four equivalent Ni(3) atoms to form a mixture of edge, face, and corner-sharing NiY4Ni8 cuboctahedra. Both Ni(11)-Ni(11) bond lengths are 2.44 Å.