CaNi2Zn3 crystallizes in the hexagonal P6/mmm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted hexagonal planar geometry to six equivalent Ni(1) atoms. In the second Ca site, Ca(2) is bonded in a 18-coordinate geometry to six equivalent Ni(1), six equivalent Zn(1), and six equivalent Zn(2) atoms. Ni(1) is bonded in a 9-coordinate geometry to one Ca(1), two equivalent Ca(2), two equivalent Zn(1), and four equivalent Zn(2) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to four equivalent Ca(2) and four equivalent Ni(1) atoms to form a mixture of distorted face, corner, and edge-sharing ZnCa4Ni4 cuboctahedra. In the second Zn site, Zn(2) is bonded in a 4-coordinate geometry to two equivalent Ca(2) and four equivalent Ni(1) atoms.
CaNi2Zn3 crystallizes in the hexagonal P6/mmm space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a distorted hexagonal planar geometry to six equivalent Ni(1) atoms. All Ca(1)-Ni(1) bond lengths are 2.81 Å. In the second Ca site, Ca(2) is bonded in a 18-coordinate geometry to six equivalent Ni(1), six equivalent Zn(1), and six equivalent Zn(2) atoms. All Ca(2)-Ni(1) bond lengths are 3.09 Å. All Ca(2)-Zn(1) bond lengths are 3.27 Å. All Ca(2)-Zn(2) bond lengths are 3.18 Å. Ni(1) is bonded in a 9-coordinate geometry to one Ca(1), two equivalent Ca(2), two equivalent Zn(1), and four equivalent Zn(2) atoms. Both Ni(1)-Zn(1) bond lengths are 2.47 Å. All Ni(1)-Zn(2) bond lengths are 2.46 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to four equivalent Ca(2) and four equivalent Ni(1) atoms to form a mixture of distorted face, corner, and edge-sharing ZnCa4Ni4 cuboctahedra. In the second Zn site, Zn(2) is bonded in a 4-coordinate geometry to two equivalent Ca(2) and four equivalent Ni(1) atoms.