Zr6Ni20P13 crystallizes in the hexagonal P-6 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 15-coordinate geometry to one Ni(7), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(6), two equivalent Ni(8), two equivalent P(3), and four equivalent P(5) atoms. In the second Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Ni(4), one Ni(8), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(5), two equivalent Ni(7), two equivalent P(2), and four equivalent P(4) atoms. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Zr(1), two equivalent Zr(2), one P(3), one P(5), and two equivalent P(4) atoms to form distorted NiZr4P4 tetrahedra that share  a cornercorner with one Ni(4)ZrP4 tetrahedra, corners with two equivalent Ni(7)Zr3P4 tetrahedra, corners with two equivalent Ni(1)Zr4P4 tetrahedra, corners with four equivalent Ni(2)Zr4P4 tetrahedra,  an edgeedge with one Ni(4)ZrP4 tetrahedra, edges with two equivalent Ni(1)Zr4P4 tetrahedra, faces with two equivalent Ni(7)Zr3P4 tetrahedra, and faces with two equivalent Ni(2)Zr4P4 tetrahedra. In the second Ni site, Ni(2) is bonded to two equivalent Zr(1), two equivalent Zr(2), one P(2), one P(4), and two equivalent P(5) atoms to form distorted NiZr4P4 tetrahedra that share corners with two equivalent Ni(2)Zr4P4 tetrahedra, corners with three equivalent Ni(7)Zr3P4 tetrahedra, corners with four equivalent Ni(1)Zr4P4 tetrahedra,  an edgeedge with one Ni(7)Zr3P4 tetrahedra, edges with two equivalent Ni(2)Zr4P4 tetrahedra, edges with two equivalent Ni(4)ZrP4 tetrahedra,  a faceface with one Ni(7)Zr3P4 tetrahedra, and faces with two equivalent Ni(1)Zr4P4 tetrahedra. In the third Ni site, Ni(3) is bonded in a 5-coordinate geometry to one P(2), two equivalent P(1), and two equivalent P(3) atoms. In the fourth Ni site, Ni(4) is bonded to one Zr(2), one P(1), one P(3), and two equivalent P(2) atoms to form distorted NiZrP4 tetrahedra that share  a cornercorner with one Ni(1)Zr4P4 tetrahedra, corners with four equivalent Ni(4)ZrP4 tetrahedra,  an edgeedge with one Ni(1)Zr4P4 tetrahedra, edges with two equivalent Ni(2)Zr4P4 tetrahedra, and faces with two equivalent Ni(7)Zr3P4 tetrahedra. In the fifth Ni site, Ni(5) is bonded in a distorted trigonal planar geometry to six equivalent Zr(2) and three equivalent P(4) atoms. In the sixth Ni site, Ni(6) is bonded in a distorted trigonal planar geometry to six equivalent Zr(1) and three equivalent P(5) atoms. In the seventh Ni site, Ni(7) is bonded to one Zr(1), two equivalent Zr(2), one P(2), one P(4), and two equivalent P(3) atoms to form distorted NiZr3P4 tetrahedra that share corners with two equivalent Ni(1)Zr4P4 tetrahedra, corners with three equivalent Ni(2)Zr4P4 tetrahedra,  an edgeedge with one Ni(2)Zr4P4 tetrahedra, edges with two equivalent Ni(7)Zr3P4 tetrahedra,  a faceface with one Ni(2)Zr4P4 tetrahedra, faces with two equivalent Ni(1)Zr4P4 tetrahedra, and faces with two equivalent Ni(4)ZrP4 tetrahedra. In the eighth Ni site, Ni(8) is bonded in a 4-coordinate geometry to one Zr(2), two equivalent Zr(1), one P(3), one P(5), and two equivalent P(2) atoms. There are five inequivalent P sites. In the first P site, P(4) is bonded in a 9-coordinate geometry to four equivalent Zr(2), one Ni(2), one Ni(5), one Ni(7), and two equivalent Ni(1) atoms. In the second P site, P(5) is bonded in a 9-coordinate geometry to four equivalent Zr(1), one Ni(1), one Ni(6), one Ni(8), and two equivalent Ni(2) atoms. In the third P site, P(1) is bonded in a 9-coordinate geometry to three equivalent Ni(4) and six equivalent Ni(3) atoms. In the fourth P site, P(2) is bonded in a 9-coordinate geometry to two equivalent Zr(2), one Ni(2), one Ni(3), one Ni(7), two equivalent Ni(4), and two equivalent Ni(8) atoms. In the fifth P site, P(3) is bonded in a 9-coordinate geometry to two equivalent Zr(1), one Ni(1), one Ni(4), one Ni(8), two equivalent Ni(3), and two equivalent Ni(7) atoms.
Zr6Ni20P13 crystallizes in the hexagonal P-6 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 15-coordinate geometry to one Ni(7), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(6), two equivalent Ni(8), two equivalent P(3), and four equivalent P(5) atoms. The Zr(1)-Ni(7) bond length is 3.05 Å. Both Zr(1)-Ni(1) bond lengths are 2.97 Å. There is one shorter (3.04 Å) and one longer (3.05 Å) Zr(1)-Ni(2) bond length. Both Zr(1)-Ni(6) bond lengths are 2.81 Å. Both Zr(1)-Ni(8) bond lengths are 2.90 Å. Both Zr(1)-P(3) bond lengths are 2.76 Å. There are two shorter (2.79 Å) and two longer (2.83 Å) Zr(1)-P(5) bond lengths. In the second Zr site, Zr(2) is bonded in a 16-coordinate geometry to one Ni(4), one Ni(8), two equivalent Ni(1), two equivalent Ni(2), two equivalent Ni(5), two equivalent Ni(7), two equivalent P(2), and four equivalent P(4) atoms. The Zr(2)-Ni(4) bond length is 2.99 Å. The Zr(2)-Ni(8) bond length is 3.13 Å. There is one shorter (3.02 Å) and one longer (3.05 Å) Zr(2)-Ni(1) bond length. Both Zr(2)-Ni(2) bond lengths are 2.97 Å. Both Zr(2)-Ni(5) bond lengths are 2.81 Å. Both Zr(2)-Ni(7) bond lengths are 2.95 Å. Both Zr(2)-P(2) bond lengths are 2.77 Å. There are two shorter (2.79 Å) and two longer (2.83 Å) Zr(2)-P(4) bond lengths. There are eight inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Zr(1), two equivalent Zr(2), one P(3), one P(5), and two equivalent P(4) atoms to form distorted NiZr4P4 tetrahedra that share  a cornercorner with one Ni(4)ZrP4 tetrahedra, corners with two equivalent Ni(7)Zr3P4 tetrahedra, corners with two equivalent Ni(1)Zr4P4 tetrahedra, corners with four equivalent Ni(2)Zr4P4 tetrahedra,  an edgeedge with one Ni(4)ZrP4 tetrahedra, edges with two equivalent Ni(1)Zr4P4 tetrahedra, faces with two equivalent Ni(7)Zr3P4 tetrahedra, and faces with two equivalent Ni(2)Zr4P4 tetrahedra. The Ni(1)-P(3) bond length is 2.22 Å. The Ni(1)-P(5) bond length is 2.24 Å. Both Ni(1)-P(4) bond lengths are 2.25 Å. In the second Ni site, Ni(2) is bonded to two equivalent Zr(1), two equivalent Zr(2), one P(2), one P(4), and two equivalent P(5) atoms to form distorted NiZr4P4 tetrahedra that share corners with two equivalent Ni(2)Zr4P4 tetrahedra, corners with three equivalent Ni(7)Zr3P4 tetrahedra, corners with four equivalent Ni(1)Zr4P4 tetrahedra,  an edgeedge with one Ni(7)Zr3P4 tetrahedra, edges with two equivalent Ni(2)Zr4P4 tetrahedra, edges with two equivalent Ni(4)ZrP4 tetrahedra,  a faceface with one Ni(7)Zr3P4 tetrahedra, and faces with two equivalent Ni(1)Zr4P4 tetrahedra. The Ni(2)-P(2) bond length is 2.21 Å. The Ni(2)-P(4) bond length is 2.27 Å. Both Ni(2)-P(5) bond lengths are 2.25 Å. In the third Ni site, Ni(3) is bonded in a 5-coordinate geometry to one P(2), two equivalent P(1), and two equivalent P(3) atoms. The Ni(3)-P(2) bond length is 2.24 Å. Both Ni(3)-P(1) bond lengths are 2.50 Å. Both Ni(3)-P(3) bond lengths are 2.52 Å. In the fourth Ni site, Ni(4) is bonded to one Zr(2), one P(1), one P(3), and two equivalent P(2) atoms to form distorted NiZrP4 tetrahedra that share  a cornercorner with one Ni(1)Zr4P4 tetrahedra, corners with four equivalent Ni(4)ZrP4 tetrahedra,  an edgeedge with one Ni(1)Zr4P4 tetrahedra, edges with two equivalent Ni(2)Zr4P4 tetrahedra, and faces with two equivalent Ni(7)Zr3P4 tetrahedra. The Ni(4)-P(1) bond length is 2.13 Å. The Ni(4)-P(3) bond length is 2.20 Å. Both Ni(4)-P(2) bond lengths are 2.29 Å. In the fifth Ni site, Ni(5) is bonded in a distorted trigonal planar geometry to six equivalent Zr(2) and three equivalent P(4) atoms. All Ni(5)-P(4) bond lengths are 2.14 Å. In the sixth Ni site, Ni(6) is bonded in a distorted trigonal planar geometry to six equivalent Zr(1) and three equivalent P(5) atoms. All Ni(6)-P(5) bond lengths are 2.15 Å. In the seventh Ni site, Ni(7) is bonded to one Zr(1), two equivalent Zr(2), one P(2), one P(4), and two equivalent P(3) atoms to form distorted NiZr3P4 tetrahedra that share corners with two equivalent Ni(1)Zr4P4 tetrahedra, corners with three equivalent Ni(2)Zr4P4 tetrahedra,  an edgeedge with one Ni(2)Zr4P4 tetrahedra, edges with two equivalent Ni(7)Zr3P4 tetrahedra,  a faceface with one Ni(2)Zr4P4 tetrahedra, faces with two equivalent Ni(1)Zr4P4 tetrahedra, and faces with two equivalent Ni(4)ZrP4 tetrahedra. The Ni(7)-P(2) bond length is 2.26 Å. The Ni(7)-P(4) bond length is 2.23 Å. Both Ni(7)-P(3) bond lengths are 2.28 Å. In the eighth Ni site, Ni(8) is bonded in a 4-coordinate geometry to one Zr(2), two equivalent Zr(1), one P(3), one P(5), and two equivalent P(2) atoms. The Ni(8)-P(3) bond length is 2.18 Å. The Ni(8)-P(5) bond length is 2.22 Å. Both Ni(8)-P(2) bond lengths are 2.32 Å. There are five inequivalent P sites. In the first P site, P(4) is bonded in a 9-coordinate geometry to four equivalent Zr(2), one Ni(2), one Ni(5), one Ni(7), and two equivalent Ni(1) atoms. In the second P site, P(5) is bonded in a 9-coordinate geometry to four equivalent Zr(1), one Ni(1), one Ni(6), one Ni(8), and two equivalent Ni(2) atoms. In the third P site, P(1) is bonded in a 9-coordinate geometry to three equivalent Ni(4) and six equivalent Ni(3) atoms. In the fourth P site, P(2) is bonded in a 9-coordinate geometry to two equivalent Zr(2), one Ni(2), one Ni(3), one Ni(7), two equivalent Ni(4), and two equivalent Ni(8) atoms. In the fifth P site, P(3) is bonded in a 9-coordinate geometry to two equivalent Zr(1), one Ni(1), one Ni(4), one Ni(8), two equivalent Ni(3), and two equivalent Ni(7) atoms.