Zn(Ni2O3)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Zn(1)O6 pentagonal pyramids, edges with five equivalent Ni(1)O6 octahedra, and edges with five equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. In the second Ni site, Ni(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Ni(2)O6 octahedra, edges with five equivalent Ni(1)O6 octahedra, and  an edgeedge with one Zn(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 0-60°. Zn(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Ni(1)O6 octahedra, corners with eight equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and faces with two equivalent Zn(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 26-72°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ni(2) and four equivalent Ni(1) atoms to form ONi6 octahedra that share corners with four equivalent O(3)Ni5 square pyramids, corners with two equivalent O(4)Zn2Ni2 tetrahedra, edges with two equivalent O(1)Ni6 octahedra, edges with six equivalent O(3)Ni5 square pyramids, and edges with four equivalent O(2)Zn2Ni3 trigonal bipyramids. In the second O site, O(2) is bonded to one Ni(1), two equivalent Ni(2), and two equivalent Zn(1) atoms to form distorted OZn2Ni3 trigonal bipyramids that share corners with five equivalent O(3)Ni5 square pyramids, corners with four equivalent O(4)Zn2Ni2 tetrahedra, corners with two equivalent O(2)Zn2Ni3 trigonal bipyramids, edges with two equivalent O(1)Ni6 octahedra,  an edgeedge with one O(3)Ni5 square pyramid,  an edgeedge with one O(4)Zn2Ni2 tetrahedra, and edges with three equivalent O(2)Zn2Ni3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Ni(2) and three equivalent Ni(1) atoms to form ONi5 square pyramids that share corners with two equivalent O(1)Ni6 octahedra, corners with two equivalent O(4)Zn2Ni2 tetrahedra, corners with five equivalent O(2)Zn2Ni3 trigonal bipyramids, edges with three equivalent O(1)Ni6 octahedra, edges with four equivalent O(3)Ni5 square pyramids, and  an edgeedge with one O(2)Zn2Ni3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 6°. In the fourth O site, O(4) is bonded to two equivalent Ni(2) and two equivalent Zn(1) atoms to form OZn2Ni2 tetrahedra that share corners with two equivalent O(1)Ni6 octahedra, corners with four equivalent O(3)Ni5 square pyramids, corners with two equivalent O(4)Zn2Ni2 tetrahedra, corners with eight equivalent O(2)Zn2Ni3 trigonal bipyramids, and edges with two equivalent O(2)Zn2Ni3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 5°.
Zn(Ni2O3)2 crystallizes in the orthorhombic Cmcm space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(2), two equivalent O(1), and three equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with two equivalent Zn(1)O6 pentagonal pyramids, edges with five equivalent Ni(1)O6 octahedra, and edges with five equivalent Ni(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-12°. The Ni(1)-O(2) bond length is 1.94 Å. Both Ni(1)-O(1) bond lengths are 2.08 Å. There is one shorter (1.98 Å) and two longer (2.06 Å) Ni(1)-O(3) bond lengths. In the second Ni site, Ni(2) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form NiO6 octahedra that share corners with two equivalent Ni(1)O6 octahedra, corners with two equivalent Ni(2)O6 octahedra, corners with four equivalent Zn(1)O6 pentagonal pyramids, edges with two equivalent Ni(2)O6 octahedra, edges with five equivalent Ni(1)O6 octahedra, and  an edgeedge with one Zn(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 0-60°. The Ni(2)-O(1) bond length is 2.21 Å. The Ni(2)-O(4) bond length is 1.98 Å. Both Ni(2)-O(2) bond lengths are 2.04 Å. Both Ni(2)-O(3) bond lengths are 2.10 Å. Zn(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form distorted ZnO6 pentagonal pyramids that share corners with four equivalent Ni(1)O6 octahedra, corners with eight equivalent Ni(2)O6 octahedra, edges with two equivalent Ni(2)O6 octahedra, and faces with two equivalent Zn(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 26-72°. Both Zn(1)-O(4) bond lengths are 2.04 Å. All Zn(1)-O(2) bond lengths are 2.25 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ni(2) and four equivalent Ni(1) atoms to form ONi6 octahedra that share corners with four equivalent O(3)Ni5 square pyramids, corners with two equivalent O(4)Zn2Ni2 tetrahedra, edges with two equivalent O(1)Ni6 octahedra, edges with six equivalent O(3)Ni5 square pyramids, and edges with four equivalent O(2)Zn2Ni3 trigonal bipyramids. In the second O site, O(2) is bonded to one Ni(1), two equivalent Ni(2), and two equivalent Zn(1) atoms to form distorted OZn2Ni3 trigonal bipyramids that share corners with five equivalent O(3)Ni5 square pyramids, corners with four equivalent O(4)Zn2Ni2 tetrahedra, corners with two equivalent O(2)Zn2Ni3 trigonal bipyramids, edges with two equivalent O(1)Ni6 octahedra,  an edgeedge with one O(3)Ni5 square pyramid,  an edgeedge with one O(4)Zn2Ni2 tetrahedra, and edges with three equivalent O(2)Zn2Ni3 trigonal bipyramids. In the third O site, O(3) is bonded to two equivalent Ni(2) and three equivalent Ni(1) atoms to form ONi5 square pyramids that share corners with two equivalent O(1)Ni6 octahedra, corners with two equivalent O(4)Zn2Ni2 tetrahedra, corners with five equivalent O(2)Zn2Ni3 trigonal bipyramids, edges with three equivalent O(1)Ni6 octahedra, edges with four equivalent O(3)Ni5 square pyramids, and  an edgeedge with one O(2)Zn2Ni3 trigonal bipyramid. The corner-sharing octahedral tilt angles are 6°. In the fourth O site, O(4) is bonded to two equivalent Ni(2) and two equivalent Zn(1) atoms to form OZn2Ni2 tetrahedra that share corners with two equivalent O(1)Ni6 octahedra, corners with four equivalent O(3)Ni5 square pyramids, corners with two equivalent O(4)Zn2Ni2 tetrahedra, corners with eight equivalent O(2)Zn2Ni3 trigonal bipyramids, and edges with two equivalent O(2)Zn2Ni3 trigonal bipyramids. The corner-sharing octahedral tilt angles are 5°.