Hf2(NiP)3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 11-coordinate geometry to one Ni(2), two equivalent Ni(1), two equivalent Ni(3), one P(1), two equivalent P(2), and three equivalent P(3) atoms. In the second Hf site, Hf(2) 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 are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Hf(1), three equivalent Hf(2), one P(2), and three equivalent P(1) atoms to form distorted NiHf5P4 tetrahedra that share corners with eight equivalent P(3)Hf5Ni2 pentagonal bipyramids, edges with two equivalent P(3)Hf5Ni2 pentagonal bipyramids, and faces with four equivalent Ni(1)Hf5P4 tetrahedra. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to one Hf(1), three equivalent Hf(2), one P(1), one P(3), and two equivalent P(2) atoms. In the third Ni site, Ni(3) is bonded in a 4-coordinate geometry to two equivalent Hf(1), three equivalent Hf(2), one P(2), one P(3), and two equivalent P(1) atoms. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Hf(1), two equivalent Hf(2), one Ni(2), two equivalent Ni(3), and three equivalent Ni(1) atoms. In the second P site, P(2) is bonded in a 8-coordinate geometry to two equivalent Hf(1), two equivalent Hf(2), one Ni(1), one Ni(3), and two equivalent Ni(2) atoms. In the third P site, P(3) is bonded to two equivalent Hf(2), three equivalent Hf(1), one Ni(2), and one Ni(3) atom to form distorted PHf5Ni2 pentagonal bipyramids that share corners with eight equivalent Ni(1)Hf5P4 tetrahedra, edges with four equivalent P(3)Hf5Ni2 pentagonal bipyramids, and edges with two equivalent Ni(1)Hf5P4 tetrahedra.
Hf2(NiP)3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Hf sites. In the first Hf site, Hf(1) is bonded in a 11-coordinate geometry to one Ni(2), two equivalent Ni(1), two equivalent Ni(3), one P(1), two equivalent P(2), and three equivalent P(3) atoms. The Hf(1)-Ni(2) bond length is 2.71 Å. Both Hf(1)-Ni(1) bond lengths are 3.00 Å. Both Hf(1)-Ni(3) bond lengths are 2.87 Å. The Hf(1)-P(1) bond length is 2.60 Å. Both Hf(1)-P(2) bond lengths are 2.66 Å. There are two shorter (2.58 Å) and one longer (2.70 Å) Hf(1)-P(3) bond length. In the second Hf site, Hf(2) 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 are two shorter (2.96 Å) and one longer (3.24 Å) Hf(2)-Ni(1) bond length. There are two shorter (2.88 Å) and one longer (2.90 Å) Hf(2)-Ni(2) bond length. There is one shorter (3.01 Å) and two longer (3.10 Å) Hf(2)-Ni(3) bond lengths. Both Hf(2)-P(1) bond lengths are 2.83 Å. Both Hf(2)-P(2) bond lengths are 2.71 Å. Both Hf(2)-P(3) bond lengths are 2.68 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Hf(1), three equivalent Hf(2), one P(2), and three equivalent P(1) atoms to form distorted NiHf5P4 tetrahedra that share corners with eight equivalent P(3)Hf5Ni2 pentagonal bipyramids, edges with two equivalent P(3)Hf5Ni2 pentagonal bipyramids, and faces with four equivalent Ni(1)Hf5P4 tetrahedra. The Ni(1)-P(2) bond length is 2.26 Å. There is one shorter (2.23 Å) and two longer (2.31 Å) Ni(1)-P(1) bond lengths. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to one Hf(1), three equivalent Hf(2), one P(1), one P(3), and two equivalent P(2) atoms. The Ni(2)-P(1) bond length is 2.24 Å. The Ni(2)-P(3) bond length is 2.18 Å. Both Ni(2)-P(2) bond lengths are 2.25 Å. In the third Ni site, Ni(3) is bonded in a 4-coordinate geometry to two equivalent Hf(1), three equivalent Hf(2), one P(2), one P(3), and two equivalent P(1) atoms. The Ni(3)-P(2) bond length is 2.32 Å. The Ni(3)-P(3) bond length is 2.24 Å. Both Ni(3)-P(1) bond lengths are 2.30 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one Hf(1), two equivalent Hf(2), one Ni(2), two equivalent Ni(3), and three equivalent Ni(1) atoms. In the second P site, P(2) is bonded in a 8-coordinate geometry to two equivalent Hf(1), two equivalent Hf(2), one Ni(1), one Ni(3), and two equivalent Ni(2) atoms. In the third P site, P(3) is bonded to two equivalent Hf(2), three equivalent Hf(1), one Ni(2), and one Ni(3) atom to form distorted PHf5Ni2 pentagonal bipyramids that share corners with eight equivalent Ni(1)Hf5P4 tetrahedra, edges with four equivalent P(3)Hf5Ni2 pentagonal bipyramids, and edges with two equivalent Ni(1)Hf5P4 tetrahedra.