V3NiP2 crystallizes in the monoclinic Pm space group. There are nine inequivalent V sites. In the first V site, V(1) is bonded to one P(2), one P(4), and two equivalent P(5) atoms to form a mixture of distorted edge and corner-sharing VP4 tetrahedra. In the second V site, V(2) is bonded to one P(1), one P(3), and two equivalent P(5) atoms to form a mixture of distorted edge and corner-sharing VP4 tetrahedra. In the third V site, V(3) is bonded in a 4-coordinate geometry to one P(2), one P(4), and two equivalent P(6) atoms. In the fourth V site, V(4) is bonded in a 7-coordinate geometry to two equivalent Ni(1), one P(5), two equivalent P(2), and two equivalent P(3) atoms. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one P(6), two equivalent P(1), and two equivalent P(4) atoms. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one P(5), two equivalent P(1), and two equivalent P(3) atoms. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one P(6), two equivalent P(2), and two equivalent P(4) atoms. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one P(6), two equivalent P(1), and two equivalent P(3) atoms. In the ninth V site, V(9) is bonded in a 5-coordinate geometry to one P(5), two equivalent P(2), and two equivalent P(4) atoms. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to two equivalent V(4), one P(2), one P(3), and two equivalent P(5) atoms. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to one P(1), one P(4), and two equivalent P(6) atoms. In the third Ni site, Ni(3) is bonded in a 4-coordinate geometry to one P(1), one P(3), and two equivalent P(6) atoms. There are six inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one V(2), two equivalent V(5), two equivalent V(6), two equivalent V(8), one Ni(2), and one Ni(3) atom. In the second P site, P(2) is bonded in a 9-coordinate geometry to one V(1), one V(3), two equivalent V(4), two equivalent V(7), two equivalent V(9), and one Ni(1) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to one V(2), two equivalent V(4), two equivalent V(6), two equivalent V(8), one Ni(1), and one Ni(3) atom. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one V(1), one V(3), two equivalent V(5), two equivalent V(7), two equivalent V(9), and one Ni(2) atom. In the fifth P site, P(5) is bonded in a 9-coordinate geometry to one V(4), one V(6), one V(9), two equivalent V(1), two equivalent V(2), and two equivalent Ni(1) atoms. In the sixth P site, P(6) is bonded in a 9-coordinate geometry to one V(5), one V(7), one V(8), two equivalent V(3), two equivalent Ni(2), and two equivalent Ni(3) atoms.
V3NiP2 crystallizes in the monoclinic Pm space group. There are nine inequivalent V sites. In the first V site, V(1) is bonded to one P(2), one P(4), and two equivalent P(5) atoms to form a mixture of distorted edge and corner-sharing VP4 tetrahedra. The V(1)-P(2) bond length is 2.36 Å. The V(1)-P(4) bond length is 2.37 Å. Both V(1)-P(5) bond lengths are 2.33 Å. In the second V site, V(2) is bonded to one P(1), one P(3), and two equivalent P(5) atoms to form a mixture of distorted edge and corner-sharing VP4 tetrahedra. The V(2)-P(1) bond length is 2.38 Å. The V(2)-P(3) bond length is 2.39 Å. Both V(2)-P(5) bond lengths are 2.33 Å. In the third V site, V(3) is bonded in a 4-coordinate geometry to one P(2), one P(4), and two equivalent P(6) atoms. The V(3)-P(2) bond length is 2.42 Å. The V(3)-P(4) bond length is 2.38 Å. Both V(3)-P(6) bond lengths are 2.35 Å. In the fourth V site, V(4) is bonded in a 7-coordinate geometry to two equivalent Ni(1), one P(5), two equivalent P(2), and two equivalent P(3) atoms. Both V(4)-Ni(1) bond lengths are 2.69 Å. The V(4)-P(5) bond length is 2.55 Å. Both V(4)-P(2) bond lengths are 2.52 Å. Both V(4)-P(3) bond lengths are 2.53 Å. In the fifth V site, V(5) is bonded in a 5-coordinate geometry to one P(6), two equivalent P(1), and two equivalent P(4) atoms. The V(5)-P(6) bond length is 2.51 Å. Both V(5)-P(1) bond lengths are 2.49 Å. Both V(5)-P(4) bond lengths are 2.49 Å. In the sixth V site, V(6) is bonded in a 5-coordinate geometry to one P(5), two equivalent P(1), and two equivalent P(3) atoms. The V(6)-P(5) bond length is 2.46 Å. Both V(6)-P(1) bond lengths are 2.48 Å. Both V(6)-P(3) bond lengths are 2.50 Å. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one P(6), two equivalent P(2), and two equivalent P(4) atoms. The V(7)-P(6) bond length is 2.60 Å. Both V(7)-P(2) bond lengths are 2.50 Å. Both V(7)-P(4) bond lengths are 2.51 Å. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one P(6), two equivalent P(1), and two equivalent P(3) atoms. The V(8)-P(6) bond length is 2.38 Å. Both V(8)-P(1) bond lengths are 2.50 Å. Both V(8)-P(3) bond lengths are 2.50 Å. In the ninth V site, V(9) is bonded in a 5-coordinate geometry to one P(5), two equivalent P(2), and two equivalent P(4) atoms. The V(9)-P(5) bond length is 2.53 Å. Both V(9)-P(2) bond lengths are 2.52 Å. Both V(9)-P(4) bond lengths are 2.47 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded in a 4-coordinate geometry to two equivalent V(4), one P(2), one P(3), and two equivalent P(5) atoms. The Ni(1)-P(2) bond length is 2.26 Å. The Ni(1)-P(3) bond length is 2.31 Å. Both Ni(1)-P(5) bond lengths are 2.22 Å. In the second Ni site, Ni(2) is bonded in a 4-coordinate geometry to one P(1), one P(4), and two equivalent P(6) atoms. The Ni(2)-P(1) bond length is 2.27 Å. The Ni(2)-P(4) bond length is 2.24 Å. Both Ni(2)-P(6) bond lengths are 2.26 Å. In the third Ni site, Ni(3) is bonded in a 4-coordinate geometry to one P(1), one P(3), and two equivalent P(6) atoms. The Ni(3)-P(1) bond length is 2.28 Å. The Ni(3)-P(3) bond length is 2.29 Å. Both Ni(3)-P(6) bond lengths are 2.26 Å. There are six inequivalent P sites. In the first P site, P(1) is bonded in a 9-coordinate geometry to one V(2), two equivalent V(5), two equivalent V(6), two equivalent V(8), one Ni(2), and one Ni(3) atom. In the second P site, P(2) is bonded in a 9-coordinate geometry to one V(1), one V(3), two equivalent V(4), two equivalent V(7), two equivalent V(9), and one Ni(1) atom. In the third P site, P(3) is bonded in a 9-coordinate geometry to one V(2), two equivalent V(4), two equivalent V(6), two equivalent V(8), one Ni(1), and one Ni(3) atom. In the fourth P site, P(4) is bonded in a 9-coordinate geometry to one V(1), one V(3), two equivalent V(5), two equivalent V(7), two equivalent V(9), and one Ni(2) atom. In the fifth P site, P(5) is bonded in a 9-coordinate geometry to one V(4), one V(6), one V(9), two equivalent V(1), two equivalent V(2), and two equivalent Ni(1) atoms. In the sixth P site, P(6) is bonded in a 9-coordinate geometry to one V(5), one V(7), one V(8), two equivalent V(3), two equivalent Ni(2), and two equivalent Ni(3) atoms.