Ni3Zn2O8 crystallizes in the hexagonal P6_3mc space group. Ni(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra,  an edgeedge with one Zn(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second Zn site, Zn(2) is bonded to one O(4) and three equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(1)O6 octahedra and corners with nine equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Ni(1) and one Zn(1) atom. In the second O site, O(2) is bonded to two equivalent Ni(1), one Zn(1), and one Zn(2) atom to form distorted OZn2Ni2 tetrahedra that share corners with two equivalent O(2)Zn2Ni2 tetrahedra,  a cornercorner with one O(4)ZnNi3 trigonal pyramid, edges with two equivalent O(2)Zn2Ni2 tetrahedra, and  an edgeedge with one O(4)ZnNi3 trigonal pyramid. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ni(1) atoms. In the fourth O site, O(4) is bonded to three equivalent Ni(1) and one Zn(2) atom to form a mixture of distorted corner and edge-sharing OZnNi3 trigonal pyramids.
Ni3Zn2O8 crystallizes in the hexagonal P6_3mc space group. Ni(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form NiO6 octahedra that share corners with two equivalent Zn(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra,  an edgeedge with one Zn(1)O6 octahedra, and edges with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The Ni(1)-O(3) bond length is 1.90 Å. The Ni(1)-O(4) bond length is 1.94 Å. Both Ni(1)-O(1) bond lengths are 1.87 Å. Both Ni(1)-O(2) bond lengths are 1.91 Å. There are two inequivalent Zn sites. In the first Zn site, Zn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form ZnO6 octahedra that share corners with six equivalent Ni(1)O6 octahedra, corners with three equivalent Zn(2)O4 tetrahedra, and edges with three equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. All Zn(1)-O(1) bond lengths are 2.02 Å. All Zn(1)-O(2) bond lengths are 2.15 Å. In the second Zn site, Zn(2) is bonded to one O(4) and three equivalent O(2) atoms to form ZnO4 tetrahedra that share corners with three equivalent Zn(1)O6 octahedra and corners with nine equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-63°. The Zn(2)-O(4) bond length is 2.07 Å. All Zn(2)-O(2) bond lengths are 1.91 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to two equivalent Ni(1) and one Zn(1) atom. In the second O site, O(2) is bonded to two equivalent Ni(1), one Zn(1), and one Zn(2) atom to form distorted OZn2Ni2 tetrahedra that share corners with two equivalent O(2)Zn2Ni2 tetrahedra,  a cornercorner with one O(4)ZnNi3 trigonal pyramid, edges with two equivalent O(2)Zn2Ni2 tetrahedra, and  an edgeedge with one O(4)ZnNi3 trigonal pyramid. In the third O site, O(3) is bonded in a distorted trigonal non-coplanar geometry to three equivalent Ni(1) atoms. In the fourth O site, O(4) is bonded to three equivalent Ni(1) and one Zn(2) atom to form a mixture of distorted corner and edge-sharing OZnNi3 trigonal pyramids.