Zr2Ni3P3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 15-coordinate geometry to three equivalent Ni(1), three equivalent Ni(2), three equivalent Ni(3), two equivalent P(1), two equivalent P(2), and two equivalent P(3) atoms. In the second Zr site, Zr(2) is bonded in a 11-coordinate geometry to one Ni(2), two equivalent Ni(1), two equivalent Ni(3), one P(2), two equivalent P(3), and three equivalent P(1) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to two equivalent Zr(2), three equivalent Zr(1), one P(1), one P(3), and two equivalent P(2) atoms. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to one Zr(2), three equivalent Zr(1), one P(1), one P(2), and two equivalent P(3) atoms. In the third Ni site, Ni(3) is bonded to two equivalent Zr(2), three equivalent Zr(1), one P(3), and three equivalent P(2) atoms to form distorted NiZr5P4 tetrahedra that share corners with eight equivalent P(1)Zr5Ni2 pentagonal bipyramids, edges with two equivalent P(1)Zr5Ni2 pentagonal bipyramids, and faces with four equivalent Ni(3)Zr5P4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to two equivalent Zr(1), three equivalent Zr(2), one Ni(1), and one Ni(2) atom to form distorted PZr5Ni2 pentagonal bipyramids that share corners with eight equivalent Ni(3)Zr5P4 tetrahedra, edges with four equivalent P(1)Zr5Ni2 pentagonal bipyramids, and edges with two equivalent Ni(3)Zr5P4 tetrahedra. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Zr(2), two equivalent Zr(1), one Ni(2), two equivalent Ni(1), and three equivalent Ni(3) atoms. In the third P site, P(3) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), one Ni(1), one Ni(3), and two equivalent Ni(2) atoms.
Zr2Ni3P3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 15-coordinate geometry to three equivalent Ni(1), three equivalent Ni(2), three equivalent Ni(3), two equivalent P(1), two equivalent P(2), and two equivalent P(3) atoms. There is one shorter (3.03 Å) and two longer (3.12 Å) Zr(1)-Ni(1) bond lengths. There are two shorter (2.91 Å) and one longer (2.92 Å) Zr(1)-Ni(2) bond length. There are two shorter (2.99 Å) and one longer (3.24 Å) Zr(1)-Ni(3) bond length. Both Zr(1)-P(1) bond lengths are 2.70 Å. Both Zr(1)-P(2) bond lengths are 2.85 Å. Both Zr(1)-P(3) bond lengths are 2.74 Å. In the second Zr site, Zr(2) is bonded in a 11-coordinate geometry to one Ni(2), two equivalent Ni(1), two equivalent Ni(3), one P(2), two equivalent P(3), and three equivalent P(1) atoms. The Zr(2)-Ni(2) bond length is 2.74 Å. Both Zr(2)-Ni(1) bond lengths are 2.91 Å. Both Zr(2)-Ni(3) bond lengths are 3.02 Å. The Zr(2)-P(2) bond length is 2.63 Å. Both Zr(2)-P(3) bond lengths are 2.69 Å. There are two shorter (2.60 Å) and one longer (2.73 Å) Zr(2)-P(1) bond length. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to two equivalent Zr(2), three equivalent Zr(1), one P(1), one P(3), and two equivalent P(2) atoms. The Ni(1)-P(1) bond length is 2.25 Å. The Ni(1)-P(3) bond length is 2.31 Å. Both Ni(1)-P(2) bond lengths are 2.33 Å. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to one Zr(2), three equivalent Zr(1), one P(1), one P(2), and two equivalent P(3) atoms. The Ni(2)-P(1) bond length is 2.19 Å. The Ni(2)-P(2) bond length is 2.25 Å. Both Ni(2)-P(3) bond lengths are 2.26 Å. In the third Ni site, Ni(3) is bonded to two equivalent Zr(2), three equivalent Zr(1), one P(3), and three equivalent P(2) atoms to form distorted NiZr5P4 tetrahedra that share corners with eight equivalent P(1)Zr5Ni2 pentagonal bipyramids, edges with two equivalent P(1)Zr5Ni2 pentagonal bipyramids, and faces with four equivalent Ni(3)Zr5P4 tetrahedra. The Ni(3)-P(3) bond length is 2.30 Å. There is one shorter (2.24 Å) and two longer (2.32 Å) Ni(3)-P(2) bond lengths. There are three inequivalent P sites. In the first P site, P(1) is bonded to two equivalent Zr(1), three equivalent Zr(2), one Ni(1), and one Ni(2) atom to form distorted PZr5Ni2 pentagonal bipyramids that share corners with eight equivalent Ni(3)Zr5P4 tetrahedra, edges with four equivalent P(1)Zr5Ni2 pentagonal bipyramids, and edges with two equivalent Ni(3)Zr5P4 tetrahedra. In the second P site, P(2) is bonded in a 9-coordinate geometry to one Zr(2), two equivalent Zr(1), one Ni(2), two equivalent Ni(1), and three equivalent Ni(3) atoms. In the third P site, P(3) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), one Ni(1), one Ni(3), and two equivalent Ni(2) atoms.