Zr4Ni3As8 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 10-coordinate geometry to two equivalent Ni(2), two equivalent As(3), two equivalent As(4), and four equivalent As(1) atoms. In the second Zr site, Zr(2) is bonded to four equivalent Ni(1,3); two equivalent As(3); two equivalent As(4); and four equivalent As(2) atoms to form distorted ZrNi4As8 cuboctahedra that share corners with four equivalent Zr(2)Ni4As8 cuboctahedra; corners with eight equivalent Ni(1,3)Zr4As4 tetrahedra; edges with four equivalent Zr(2)Ni4As8 cuboctahedra; edges with four equivalent Ni(1,3)Zr4As4 tetrahedra; and faces with four equivalent Zr(2)Ni4As8 cuboctahedra. There are two inequivalent Ni sites. In the first Ni site, Ni(1,3) is bonded to four equivalent Zr(2) and four equivalent As(2) atoms to form distorted NiZr4As4 tetrahedra that share corners with eight equivalent Zr(2)Ni4As8 cuboctahedra; edges with four equivalent Zr(2)Ni4As8 cuboctahedra; edges with four equivalent Ni(1,3)Zr4As4 tetrahedra; and faces with four equivalent Ni(1,3)Zr4As4 tetrahedra. In the second Ni site, Ni(2) is bonded to four equivalent Zr(1) and four equivalent As(1) atoms to form distorted edge-sharing NiZr4As4 tetrahedra. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 6-coordinate geometry to four equivalent Zr(1) and two equivalent Ni(2) atoms. In the second As site, As(2) is bonded in a 8-coordinate geometry to four equivalent Zr(2) and four equivalent Ni(1,3) atoms. In the third As site, As(3) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent As(4) atoms. In the fourth As site, As(4) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent As(3) atoms.
Zr4Ni3As8 crystallizes in the tetragonal P-4m2 space group. There are two inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 10-coordinate geometry to two equivalent Ni(2), two equivalent As(3), two equivalent As(4), and four equivalent As(1) atoms. Both Zr(1)-Ni(2) bond lengths are 2.89 Å. Both Zr(1)-As(3) bond lengths are 2.87 Å. Both Zr(1)-As(4) bond lengths are 2.87 Å. All Zr(1)-As(1) bond lengths are 2.85 Å. In the second Zr site, Zr(2) is bonded to four equivalent Ni(1,3); two equivalent As(3); two equivalent As(4); and four equivalent As(2) atoms to form distorted ZrNi4As8 cuboctahedra that share corners with four equivalent Zr(2)Ni4As8 cuboctahedra; corners with eight equivalent Ni(1,3)Zr4As4 tetrahedra; edges with four equivalent Zr(2)Ni4As8 cuboctahedra; edges with four equivalent Ni(1,3)Zr4As4 tetrahedra; and faces with four equivalent Zr(2)Ni4As8 cuboctahedra. All Zr(2)-Ni(1,3) bond lengths are 3.03 Å. Both Zr(2)-As(3) bond lengths are 2.87 Å. Both Zr(2)-As(4) bond lengths are 2.87 Å. All Zr(2)-As(2) bond lengths are 2.85 Å. There are two inequivalent Ni sites. In the first Ni site, Ni(1,3) is bonded to four equivalent Zr(2) and four equivalent As(2) atoms to form distorted NiZr4As4 tetrahedra that share corners with eight equivalent Zr(2)Ni4As8 cuboctahedra; edges with four equivalent Zr(2)Ni4As8 cuboctahedra; edges with four equivalent Ni(1,3)Zr4As4 tetrahedra; and faces with four equivalent Ni(1,3)Zr4As4 tetrahedra. All Ni(1,3)-As(2) bond lengths are 2.37 Å. In the second Ni site, Ni(2) is bonded to four equivalent Zr(1) and four equivalent As(1) atoms to form distorted edge-sharing NiZr4As4 tetrahedra. All Ni(2)-As(1) bond lengths are 2.27 Å. There are four inequivalent As sites. In the first As site, As(1) is bonded in a 6-coordinate geometry to four equivalent Zr(1) and two equivalent Ni(2) atoms. In the second As site, As(2) is bonded in a 8-coordinate geometry to four equivalent Zr(2) and four equivalent Ni(1,3) atoms. In the third As site, As(3) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent As(4) atoms. All As(3)-As(4) bond lengths are 2.69 Å. In the fourth As site, As(4) is bonded in a 8-coordinate geometry to two equivalent Zr(1), two equivalent Zr(2), and four equivalent As(3) atoms.