Ni3Zn3(AsO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(4), one O(7), and one O(8) atom to form NiO5 trigonal bipyramids that share corners with two equivalent As(2)O4 tetrahedra, corners with three equivalent As(1)O4 tetrahedra, and  an edgeedge with one Zn(2)O6 octahedra. In the second Ni site, Ni(2) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(7) atoms. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and one O(7) atom. In the second Zn site, Zn(2) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form ZnO6 octahedra that share corners with two equivalent As(2)O4 tetrahedra, corners with four equivalent As(1)O4 tetrahedra, and edges with two equivalent Ni(1)O5 trigonal bipyramids. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form AsO4 tetrahedra that share corners with two equivalent Zn(2)O6 octahedra and corners with three equivalent Ni(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 48-58°. In the second As site, As(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form AsO4 tetrahedra that share  a cornercorner with one Zn(2)O6 octahedra and corners with two equivalent Ni(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 58°. There are eight inequivalent O sites. In the first O site, O(7) is bonded to one Ni(1), one Ni(2), one Zn(1), and one As(2) atom to form corner-sharing OZnNi2As tetrahedra. In the second O site, O(8) is bonded in a distorted trigonal planar geometry to one Ni(1), one Zn(2), and one As(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Ni(1), one Zn(1), and one As(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Ni(1), one Zn(2), and one As(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Zn(1) and one As(2) atom. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Ni(1), one Zn(1), and one As(1) atom. In the seventh O site, O(5) is bonded in a 2-coordinate geometry to one Ni(2), one Zn(1), and one As(2) atom. In the eighth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(2) and one As(1) atom.
Ni3Zn3(AsO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one O(2), one O(4), one O(7), and one O(8) atom to form NiO5 trigonal bipyramids that share corners with two equivalent As(2)O4 tetrahedra, corners with three equivalent As(1)O4 tetrahedra, and  an edgeedge with one Zn(2)O6 octahedra. The Ni(1)-O(1) bond length is 2.01 Å. The Ni(1)-O(2) bond length is 2.03 Å. The Ni(1)-O(4) bond length is 2.02 Å. The Ni(1)-O(7) bond length is 2.12 Å. The Ni(1)-O(8) bond length is 2.11 Å. In the second Ni site, Ni(2) is bonded in a square co-planar geometry to two equivalent O(5) and two equivalent O(7) atoms. Both Ni(2)-O(5) bond lengths are 1.97 Å. Both Ni(2)-O(7) bond lengths are 2.00 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(4), one O(5), and one O(7) atom. The Zn(1)-O(1) bond length is 2.06 Å. The Zn(1)-O(3) bond length is 1.92 Å. The Zn(1)-O(4) bond length is 2.04 Å. The Zn(1)-O(5) bond length is 2.46 Å. The Zn(1)-O(7) bond length is 2.19 Å. In the second Zn site, Zn(2) is bonded to two equivalent O(2), two equivalent O(6), and two equivalent O(8) atoms to form ZnO6 octahedra that share corners with two equivalent As(2)O4 tetrahedra, corners with four equivalent As(1)O4 tetrahedra, and edges with two equivalent Ni(1)O5 trigonal bipyramids. Both Zn(2)-O(2) bond lengths are 2.14 Å. Both Zn(2)-O(6) bond lengths are 2.04 Å. Both Zn(2)-O(8) bond lengths are 2.23 Å. There are two inequivalent As sites. In the first As site, As(1) is bonded to one O(1), one O(4), one O(6), and one O(8) atom to form AsO4 tetrahedra that share corners with two equivalent Zn(2)O6 octahedra and corners with three equivalent Ni(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 48-58°. The As(1)-O(1) bond length is 1.75 Å. The As(1)-O(4) bond length is 1.75 Å. The As(1)-O(6) bond length is 1.69 Å. The As(1)-O(8) bond length is 1.73 Å. In the second As site, As(2) is bonded to one O(2), one O(3), one O(5), and one O(7) atom to form AsO4 tetrahedra that share  a cornercorner with one Zn(2)O6 octahedra and corners with two equivalent Ni(1)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 58°. The As(2)-O(2) bond length is 1.72 Å. The As(2)-O(3) bond length is 1.69 Å. The As(2)-O(5) bond length is 1.72 Å. The As(2)-O(7) bond length is 1.79 Å. There are eight inequivalent O sites. In the first O site, O(7) is bonded to one Ni(1), one Ni(2), one Zn(1), and one As(2) atom to form corner-sharing OZnNi2As tetrahedra. In the second O site, O(8) is bonded in a distorted trigonal planar geometry to one Ni(1), one Zn(2), and one As(1) atom. In the third O site, O(1) is bonded in a distorted trigonal planar geometry to one Ni(1), one Zn(1), and one As(1) atom. In the fourth O site, O(2) is bonded in a distorted trigonal planar geometry to one Ni(1), one Zn(2), and one As(2) atom. In the fifth O site, O(3) is bonded in a bent 150 degrees geometry to one Zn(1) and one As(2) atom. In the sixth O site, O(4) is bonded in a trigonal planar geometry to one Ni(1), one Zn(1), and one As(1) atom. In the seventh O site, O(5) is bonded in a 2-coordinate geometry to one Ni(2), one Zn(1), and one As(2) atom. In the eighth O site, O(6) is bonded in a bent 120 degrees geometry to one Zn(2) and one As(1) atom.