Ni5P2 crystallizes in the hexagonal P6_3cm space group. There are six inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one P(1) and three equivalent P(3) atoms to form distorted corner-sharing NiP4 tetrahedra. In the second Ni site, Ni(2) is bonded to three equivalent Ni(4), one P(2), and three equivalent P(3) atoms to form distorted NiNi3P4 tetrahedra that share corners with three equivalent Ni(1)P4 tetrahedra and edges with three equivalent Ni(2)Ni3P4 tetrahedra. In the third Ni site, Ni(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ni(4), one P(1), and two equivalent P(3) atoms. In the fourth Ni site, Ni(4) is bonded in a 13-coordinate geometry to one Ni(6), two equivalent Ni(2), three equivalent Ni(3), three equivalent Ni(5), one P(1), one P(3), and two equivalent P(2) atoms. In the fifth Ni site, Ni(5) is bonded in a 4-coordinate geometry to three equivalent Ni(4), one P(1), one P(3), and two equivalent P(2) atoms. In the sixth Ni site, Ni(6) is bonded in a distorted single-bond geometry to one Ni(4), two equivalent P(2), and three equivalent P(3) atoms. There are three inequivalent P sites. In the first P site, P(2) is bonded in a 10-coordinate geometry to one Ni(2), three equivalent Ni(4), three equivalent Ni(5), and three equivalent Ni(6) atoms. In the second P site, P(3) is bonded in a 10-coordinate geometry to one Ni(1), one Ni(4), one Ni(5), two equivalent Ni(2), two equivalent Ni(3), and three equivalent Ni(6) atoms. In the third P site, P(1) is bonded in a 10-coordinate geometry to one Ni(1), three equivalent Ni(3), three equivalent Ni(4), and three equivalent Ni(5) atoms.
Ni5P2 crystallizes in the hexagonal P6_3cm space group. There are six inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one P(1) and three equivalent P(3) atoms to form distorted corner-sharing NiP4 tetrahedra. The Ni(1)-P(1) bond length is 2.37 Å. All Ni(1)-P(3) bond lengths are 2.30 Å. In the second Ni site, Ni(2) is bonded to three equivalent Ni(4), one P(2), and three equivalent P(3) atoms to form distorted NiNi3P4 tetrahedra that share corners with three equivalent Ni(1)P4 tetrahedra and edges with three equivalent Ni(2)Ni3P4 tetrahedra. All Ni(2)-Ni(4) bond lengths are 2.60 Å. The Ni(2)-P(2) bond length is 2.51 Å. All Ni(2)-P(3) bond lengths are 2.35 Å. In the third Ni site, Ni(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ni(4), one P(1), and two equivalent P(3) atoms. There are two shorter (2.50 Å) and one longer (2.78 Å) Ni(3)-Ni(4) bond length. The Ni(3)-P(1) bond length is 2.26 Å. Both Ni(3)-P(3) bond lengths are 2.25 Å. In the fourth Ni site, Ni(4) is bonded in a 13-coordinate geometry to one Ni(6), two equivalent Ni(2), three equivalent Ni(3), three equivalent Ni(5), one P(1), one P(3), and two equivalent P(2) atoms. The Ni(4)-Ni(6) bond length is 2.65 Å. There is one shorter (2.44 Å) and two longer (2.66 Å) Ni(4)-Ni(5) bond lengths. The Ni(4)-P(1) bond length is 2.54 Å. The Ni(4)-P(3) bond length is 2.44 Å. Both Ni(4)-P(2) bond lengths are 2.23 Å. In the fifth Ni site, Ni(5) is bonded in a 4-coordinate geometry to three equivalent Ni(4), one P(1), one P(3), and two equivalent P(2) atoms. The Ni(5)-P(1) bond length is 2.19 Å. The Ni(5)-P(3) bond length is 2.37 Å. Both Ni(5)-P(2) bond lengths are 2.32 Å. In the sixth Ni site, Ni(6) is bonded in a distorted single-bond geometry to one Ni(4), two equivalent P(2), and three equivalent P(3) atoms. Both Ni(6)-P(2) bond lengths are 2.69 Å. There is one shorter (2.17 Å) and two longer (2.57 Å) Ni(6)-P(3) bond lengths. There are three inequivalent P sites. In the first P site, P(2) is bonded in a 10-coordinate geometry to one Ni(2), three equivalent Ni(4), three equivalent Ni(5), and three equivalent Ni(6) atoms. In the second P site, P(3) is bonded in a 10-coordinate geometry to one Ni(1), one Ni(4), one Ni(5), two equivalent Ni(2), two equivalent Ni(3), and three equivalent Ni(6) atoms. In the third P site, P(1) is bonded in a 10-coordinate geometry to one Ni(1), three equivalent Ni(3), three equivalent Ni(4), and three equivalent Ni(5) atoms.