Ni3Zn22 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted q6 geometry to one Zn(3), one Zn(5), one Zn(6), two equivalent Zn(1), two equivalent Zn(2), and four equivalent Zn(8) atoms. In the second Ni site, Ni(2) is bonded in a cuboctahedral geometry to two equivalent Zn(3), two equivalent Zn(4), four equivalent Zn(1), and four equivalent Zn(7) atoms. There are eight inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 2-coordinate geometry to one Ni(1), one Ni(2), one Zn(2), one Zn(4), one Zn(5), one Zn(6), and two equivalent Zn(7) atoms. In the second Zn site, Zn(2) is bonded in a 11-coordinate geometry to two equivalent Ni(1), one Zn(2), two equivalent Zn(1), two equivalent Zn(4), two equivalent Zn(5), and two equivalent Zn(8) atoms. In the third Zn site, Zn(3) is bonded in a distorted linear geometry to one Ni(1), one Ni(2), one Zn(4), one Zn(5), and two equivalent Zn(7) atoms. In the fourth Zn site, Zn(4) is bonded in a 11-coordinate geometry to one Ni(2), one Zn(3), one Zn(4), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(7), and two equivalent Zn(8) atoms. In the fifth Zn site, Zn(5) is bonded in a 13-coordinate geometry to one Ni(1), one Zn(3), one Zn(6), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(8), and four equivalent Zn(7) atoms. In the sixth Zn site, Zn(6) is bonded in a 10-coordinate geometry to one Ni(1), one Zn(5), two equivalent Zn(1), two equivalent Zn(8), and four equivalent Zn(7) atoms. In the seventh Zn site, Zn(7) is bonded in a 12-coordinate geometry to one Ni(2), one Zn(3), one Zn(4), one Zn(8), two equivalent Zn(1), two equivalent Zn(5), two equivalent Zn(6), and two equivalent Zn(7) atoms. In the eighth Zn site, Zn(8) is bonded in a 2-coordinate geometry to two equivalent Ni(1), one Zn(2), one Zn(4), one Zn(5), one Zn(6), and one Zn(7) atom.
Ni3Zn22 crystallizes in the monoclinic C2/m space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a distorted q6 geometry to one Zn(3), one Zn(5), one Zn(6), two equivalent Zn(1), two equivalent Zn(2), and four equivalent Zn(8) atoms. The Ni(1)-Zn(3) bond length is 2.45 Å. The Ni(1)-Zn(5) bond length is 2.52 Å. The Ni(1)-Zn(6) bond length is 2.60 Å. Both Ni(1)-Zn(1) bond lengths are 2.46 Å. Both Ni(1)-Zn(2) bond lengths are 2.60 Å. There are two shorter (2.51 Å) and two longer (2.55 Å) Ni(1)-Zn(8) bond lengths. In the second Ni site, Ni(2) is bonded in a cuboctahedral geometry to two equivalent Zn(3), two equivalent Zn(4), four equivalent Zn(1), and four equivalent Zn(7) atoms. Both Ni(2)-Zn(3) bond lengths are 2.47 Å. Both Ni(2)-Zn(4) bond lengths are 2.58 Å. All Ni(2)-Zn(1) bond lengths are 2.58 Å. All Ni(2)-Zn(7) bond lengths are 2.56 Å. There are eight inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 2-coordinate geometry to one Ni(1), one Ni(2), one Zn(2), one Zn(4), one Zn(5), one Zn(6), and two equivalent Zn(7) atoms. The Zn(1)-Zn(2) bond length is 2.62 Å. The Zn(1)-Zn(4) bond length is 2.70 Å. The Zn(1)-Zn(5) bond length is 3.02 Å. The Zn(1)-Zn(6) bond length is 2.56 Å. There is one shorter (2.62 Å) and one longer (2.81 Å) Zn(1)-Zn(7) bond length. In the second Zn site, Zn(2) is bonded in a 11-coordinate geometry to two equivalent Ni(1), one Zn(2), two equivalent Zn(1), two equivalent Zn(4), two equivalent Zn(5), and two equivalent Zn(8) atoms. The Zn(2)-Zn(2) bond length is 2.58 Å. Both Zn(2)-Zn(4) bond lengths are 2.68 Å. Both Zn(2)-Zn(5) bond lengths are 2.63 Å. Both Zn(2)-Zn(8) bond lengths are 2.56 Å. In the third Zn site, Zn(3) is bonded in a distorted linear geometry to one Ni(1), one Ni(2), one Zn(4), one Zn(5), and two equivalent Zn(7) atoms. The Zn(3)-Zn(4) bond length is 2.65 Å. The Zn(3)-Zn(5) bond length is 2.58 Å. Both Zn(3)-Zn(7) bond lengths are 2.72 Å. In the fourth Zn site, Zn(4) is bonded in a 11-coordinate geometry to one Ni(2), one Zn(3), one Zn(4), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(7), and two equivalent Zn(8) atoms. The Zn(4)-Zn(4) bond length is 2.50 Å. Both Zn(4)-Zn(7) bond lengths are 2.61 Å. Both Zn(4)-Zn(8) bond lengths are 2.88 Å. In the fifth Zn site, Zn(5) is bonded in a 13-coordinate geometry to one Ni(1), one Zn(3), one Zn(6), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(8), and four equivalent Zn(7) atoms. The Zn(5)-Zn(6) bond length is 2.51 Å. Both Zn(5)-Zn(8) bond lengths are 2.79 Å. There are two shorter (2.72 Å) and two longer (2.93 Å) Zn(5)-Zn(7) bond lengths. In the sixth Zn site, Zn(6) is bonded in a 10-coordinate geometry to one Ni(1), one Zn(5), two equivalent Zn(1), two equivalent Zn(8), and four equivalent Zn(7) atoms. Both Zn(6)-Zn(8) bond lengths are 2.55 Å. There are two shorter (2.61 Å) and two longer (2.73 Å) Zn(6)-Zn(7) bond lengths. In the seventh Zn site, Zn(7) is bonded in a 12-coordinate geometry to one Ni(2), one Zn(3), one Zn(4), one Zn(8), two equivalent Zn(1), two equivalent Zn(5), two equivalent Zn(6), and two equivalent Zn(7) atoms. The Zn(7)-Zn(8) bond length is 2.95 Å. There is one shorter (2.53 Å) and one longer (2.64 Å) Zn(7)-Zn(7) bond length. In the eighth Zn site, Zn(8) is bonded in a 2-coordinate geometry to two equivalent Ni(1), one Zn(2), one Zn(4), one Zn(5), one Zn(6), and one Zn(7) atom.