Pr3Zn22 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 18-coordinate geometry to two equivalent Zn(3), two equivalent Zn(4), six equivalent Zn(2), and eight equivalent Zn(1) atoms. In the second Pr site, Pr(2) is bonded in a 20-coordinate geometry to four equivalent Zn(3), four equivalent Zn(4), four equivalent Zn(5), and eight equivalent Zn(1) atoms. There are five inequivalent Zn sites. In the first Zn site, Zn(3) is bonded to one Pr(1), one Pr(2), one Zn(3), one Zn(5), two equivalent Zn(2), two equivalent Zn(4), and four equivalent Zn(1) atoms to form distorted ZnPr2Zn10 cuboctahedra that share  a cornercorner with one Zn(5)Pr2Zn10 cuboctahedra, corners with two equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Pr3Zn9 cuboctahedra, edges with two equivalent Zn(5)Pr2Zn10 cuboctahedra, edges with two equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with three equivalent Zn(3)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(4)Pr2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Pr3Zn9 cuboctahedra. In the second Zn site, Zn(1) is bonded to one Pr(2), two equivalent Pr(1), one Zn(5), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(3), and two equivalent Zn(4) atoms to form distorted ZnPr3Zn9 cuboctahedra that share corners with two equivalent Zn(5)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with eleven equivalent Zn(1)Pr3Zn9 cuboctahedra,  an edgeedge with one Zn(3)Pr2Zn10 cuboctahedra,  an edgeedge with one Zn(4)Pr2Zn10 cuboctahedra,  an edgeedge with one Zn(5)Pr2Zn10 cuboctahedra, edges with five equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(3)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(4)Pr2Zn10 cuboctahedra, and faces with six equivalent Zn(1)Pr3Zn9 cuboctahedra. In the third Zn site, Zn(4) is bonded to one Pr(1), one Pr(2), one Zn(2), one Zn(4), two equivalent Zn(3), two equivalent Zn(5), and four equivalent Zn(1) atoms to form distorted ZnPr2Zn10 cuboctahedra that share corners with two equivalent Zn(5)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with five equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Pr3Zn9 cuboctahedra, edges with two equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with three equivalent Zn(4)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(3)Pr2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Pr3Zn9 cuboctahedra. In the fourth Zn site, Zn(5) is bonded to two equivalent Pr(2), two equivalent Zn(3), four equivalent Zn(1), and four equivalent Zn(4) atoms to form ZnPr2Zn10 cuboctahedra that share corners with two equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(5)Pr2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Pr3Zn9 cuboctahedra, edges with four equivalent Zn(3)Pr2Zn10 cuboctahedra, edges with four equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with four equivalent Zn(3)Pr2Zn10 cuboctahedra, faces with four equivalent Zn(4)Pr2Zn10 cuboctahedra, and faces with eight equivalent Zn(1)Pr3Zn9 cuboctahedra. In the fifth Zn site, Zn(2) is bonded in a 12-coordinate geometry to three equivalent Pr(1), one Zn(4), two equivalent Zn(2), two equivalent Zn(3), and four equivalent Zn(1) atoms.
Pr3Zn22 crystallizes in the tetragonal I4_1/amd space group. There are two inequivalent Pr sites. In the first Pr site, Pr(1) is bonded in a 18-coordinate geometry to two equivalent Zn(3), two equivalent Zn(4), six equivalent Zn(2), and eight equivalent Zn(1) atoms. Both Pr(1)-Zn(3) bond lengths are 3.17 Å. Both Pr(1)-Zn(4) bond lengths are 3.09 Å. There are a spread of Pr(1)-Zn(2) bond distances ranging from 3.20-3.60 Å. There are four shorter (3.27 Å) and four longer (3.41 Å) Pr(1)-Zn(1) bond lengths. In the second Pr site, Pr(2) is bonded in a 20-coordinate geometry to four equivalent Zn(3), four equivalent Zn(4), four equivalent Zn(5), and eight equivalent Zn(1) atoms. All Pr(2)-Zn(3) bond lengths are 3.12 Å. All Pr(2)-Zn(4) bond lengths are 3.22 Å. All Pr(2)-Zn(5) bond lengths are 3.43 Å. All Pr(2)-Zn(1) bond lengths are 3.33 Å. There are five inequivalent Zn sites. In the first Zn site, Zn(3) is bonded to one Pr(1), one Pr(2), one Zn(3), one Zn(5), two equivalent Zn(2), two equivalent Zn(4), and four equivalent Zn(1) atoms to form distorted ZnPr2Zn10 cuboctahedra that share  a cornercorner with one Zn(5)Pr2Zn10 cuboctahedra, corners with two equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Pr3Zn9 cuboctahedra, edges with two equivalent Zn(5)Pr2Zn10 cuboctahedra, edges with two equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with three equivalent Zn(3)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(4)Pr2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Pr3Zn9 cuboctahedra. The Zn(3)-Zn(3) bond length is 2.58 Å. The Zn(3)-Zn(5) bond length is 2.61 Å. Both Zn(3)-Zn(2) bond lengths are 2.75 Å. Both Zn(3)-Zn(4) bond lengths are 2.84 Å. There are two shorter (2.70 Å) and two longer (2.75 Å) Zn(3)-Zn(1) bond lengths. In the second Zn site, Zn(1) is bonded to one Pr(2), two equivalent Pr(1), one Zn(5), two equivalent Zn(1), two equivalent Zn(2), two equivalent Zn(3), and two equivalent Zn(4) atoms to form distorted ZnPr3Zn9 cuboctahedra that share corners with two equivalent Zn(5)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with eleven equivalent Zn(1)Pr3Zn9 cuboctahedra,  an edgeedge with one Zn(3)Pr2Zn10 cuboctahedra,  an edgeedge with one Zn(4)Pr2Zn10 cuboctahedra,  an edgeedge with one Zn(5)Pr2Zn10 cuboctahedra, edges with five equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(3)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(4)Pr2Zn10 cuboctahedra, and faces with six equivalent Zn(1)Pr3Zn9 cuboctahedra. The Zn(1)-Zn(5) bond length is 2.61 Å. There is one shorter (2.61 Å) and one longer (2.70 Å) Zn(1)-Zn(1) bond length. There is one shorter (2.53 Å) and one longer (2.74 Å) Zn(1)-Zn(2) bond length. There is one shorter (2.72 Å) and one longer (2.76 Å) Zn(1)-Zn(4) bond length. In the third Zn site, Zn(4) is bonded to one Pr(1), one Pr(2), one Zn(2), one Zn(4), two equivalent Zn(3), two equivalent Zn(5), and four equivalent Zn(1) atoms to form distorted ZnPr2Zn10 cuboctahedra that share corners with two equivalent Zn(5)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with five equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Pr3Zn9 cuboctahedra, edges with two equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with three equivalent Zn(4)Pr2Zn10 cuboctahedra, faces with five equivalent Zn(3)Pr2Zn10 cuboctahedra, and faces with ten equivalent Zn(1)Pr3Zn9 cuboctahedra. The Zn(4)-Zn(2) bond length is 2.62 Å. The Zn(4)-Zn(4) bond length is 2.65 Å. Both Zn(4)-Zn(5) bond lengths are 2.59 Å. In the fourth Zn site, Zn(5) is bonded to two equivalent Pr(2), two equivalent Zn(3), four equivalent Zn(1), and four equivalent Zn(4) atoms to form ZnPr2Zn10 cuboctahedra that share corners with two equivalent Zn(3)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(4)Pr2Zn10 cuboctahedra, corners with four equivalent Zn(5)Pr2Zn10 cuboctahedra, corners with eight equivalent Zn(1)Pr3Zn9 cuboctahedra, edges with four equivalent Zn(3)Pr2Zn10 cuboctahedra, edges with four equivalent Zn(1)Pr3Zn9 cuboctahedra, faces with two equivalent Zn(5)Pr2Zn10 cuboctahedra, faces with four equivalent Zn(3)Pr2Zn10 cuboctahedra, faces with four equivalent Zn(4)Pr2Zn10 cuboctahedra, and faces with eight equivalent Zn(1)Pr3Zn9 cuboctahedra. In the fifth Zn site, Zn(2) is bonded in a 12-coordinate geometry to three equivalent Pr(1), one Zn(4), two equivalent Zn(2), two equivalent Zn(3), and four equivalent Zn(1) atoms. Both Zn(2)-Zn(2) bond lengths are 2.81 Å.