Ca2NiWO6 is Corundum-derived structured and crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CaO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Ca(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra,  an edgeedge with one Ca(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, and edges with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-64°. W(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form WO6 octahedra that share corners with four equivalent Ca(1)O6 octahedra, edges with four equivalent Ca(1)O6 octahedra, and faces with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-41°. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NiO6 octahedra that share corners with eight equivalent Ca(1)O6 octahedra, edges with two equivalent Ca(1)O6 octahedra, and faces with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-49°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1), one W(1), and one Ni(1) atom to form a mixture of distorted corner and edge-sharing OCa2NiW trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Ca(1), one W(1), and one Ni(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ca(1), one W(1), and one Ni(1) atom.
Ca2NiWO6 is Corundum-derived structured and crystallizes in the monoclinic P2_1/c space group. Ca(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form CaO6 octahedra that share corners with two equivalent W(1)O6 octahedra, corners with four equivalent Ca(1)O6 octahedra, corners with four equivalent Ni(1)O6 octahedra,  an edgeedge with one Ca(1)O6 octahedra,  an edgeedge with one Ni(1)O6 octahedra, and edges with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-64°. Both Ca(1)-O(1) bond lengths are 2.40 Å. There is one shorter (2.37 Å) and one longer (2.43 Å) Ca(1)-O(2) bond length. There is one shorter (2.37 Å) and one longer (2.43 Å) Ca(1)-O(3) bond length. W(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form WO6 octahedra that share corners with four equivalent Ca(1)O6 octahedra, edges with four equivalent Ca(1)O6 octahedra, and faces with two equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 40-41°. Both W(1)-O(1) bond lengths are 1.94 Å. Both W(1)-O(2) bond lengths are 1.97 Å. Both W(1)-O(3) bond lengths are 1.98 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NiO6 octahedra that share corners with eight equivalent Ca(1)O6 octahedra, edges with two equivalent Ca(1)O6 octahedra, and faces with two equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-49°. Both Ni(1)-O(1) bond lengths are 2.24 Å. Both Ni(1)-O(2) bond lengths are 2.09 Å. Both Ni(1)-O(3) bond lengths are 2.09 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Ca(1), one W(1), and one Ni(1) atom to form a mixture of distorted corner and edge-sharing OCa2NiW trigonal pyramids. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to two equivalent Ca(1), one W(1), and one Ni(1) atom. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Ca(1), one W(1), and one Ni(1) atom.