CaLa4WNi3O12 crystallizes in the monoclinic P2/m space group. Ca(1) is bonded in a square co-planar geometry to two equivalent La(1), two equivalent O(3), and two equivalent O(5) atoms. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one Ca(1), two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. In the second La site, La(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. W(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Ni(3)O6 octahedra and corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. In the second Ni site, Ni(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent W(1)O6 octahedra and corners with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form corner-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), one Ni(1), and one Ni(3) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), one W(1), and one Ni(2) atom. In the third O site, O(3) is bonded to one Ca(1), two equivalent La(2), one Ni(2), and one Ni(3) atom to form a mixture of edge, face, and corner-sharing OCaLa2Ni2 trigonal bipyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent La(1), one W(1), and one Ni(1) atom. In the fifth O site, O(5) is bonded to one Ca(1), two equivalent La(2), one Ni(2), and one Ni(3) atom to form a mixture of distorted edge, face, and corner-sharing OCaLa2Ni2 trigonal bipyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent La(1), one W(1), and one Ni(1) atom.
CaLa4WNi3O12 crystallizes in the monoclinic P2/m space group. Ca(1) is bonded in a square co-planar geometry to two equivalent La(1), two equivalent O(3), and two equivalent O(5) atoms. Both Ca(1)-La(1) bond lengths are 2.95 Å. Both Ca(1)-O(3) bond lengths are 2.19 Å. Both Ca(1)-O(5) bond lengths are 2.19 Å. There are two inequivalent La sites. In the first La site, La(1) is bonded in a 9-coordinate geometry to one Ca(1), two equivalent O(1), two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms. Both La(1)-O(1) bond lengths are 2.86 Å. Both La(1)-O(2) bond lengths are 2.92 Å. Both La(1)-O(4) bond lengths are 2.36 Å. Both La(1)-O(6) bond lengths are 2.49 Å. In the second La site, La(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms. Both La(2)-O(1) bond lengths are 2.93 Å. Both La(2)-O(2) bond lengths are 2.87 Å. Both La(2)-O(3) bond lengths are 2.50 Å. Both La(2)-O(5) bond lengths are 2.52 Å. W(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(6) atoms to form WO6 octahedra that share corners with two equivalent Ni(2)O6 octahedra and corners with four equivalent Ni(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. Both W(1)-O(2) bond lengths are 2.11 Å. Both W(1)-O(4) bond lengths are 2.07 Å. Both W(1)-O(6) bond lengths are 2.01 Å. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(6) atoms to form NiO6 octahedra that share corners with two equivalent Ni(3)O6 octahedra and corners with four equivalent W(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-16°. Both Ni(1)-O(1) bond lengths are 2.32 Å. Both Ni(1)-O(4) bond lengths are 1.98 Å. Both Ni(1)-O(6) bond lengths are 1.99 Å. In the second Ni site, Ni(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form NiO6 octahedra that share corners with two equivalent W(1)O6 octahedra and corners with four equivalent Ni(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. Both Ni(2)-O(2) bond lengths are 2.46 Å. Both Ni(2)-O(3) bond lengths are 1.98 Å. Both Ni(2)-O(5) bond lengths are 1.97 Å. In the third Ni site, Ni(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(5) atoms to form corner-sharing NiO6 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. Both Ni(3)-O(1) bond lengths are 2.26 Å. Both Ni(3)-O(3) bond lengths are 2.05 Å. Both Ni(3)-O(5) bond lengths are 2.04 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), one Ni(1), and one Ni(3) atom. In the second O site, O(2) is bonded in a 6-coordinate geometry to two equivalent La(1), two equivalent La(2), one W(1), and one Ni(2) atom. In the third O site, O(3) is bonded to one Ca(1), two equivalent La(2), one Ni(2), and one Ni(3) atom to form a mixture of edge, face, and corner-sharing OCaLa2Ni2 trigonal bipyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to two equivalent La(1), one W(1), and one Ni(1) atom. In the fifth O site, O(5) is bonded to one Ca(1), two equivalent La(2), one Ni(2), and one Ni(3) atom to form a mixture of distorted edge, face, and corner-sharing OCaLa2Ni2 trigonal bipyramids. In the sixth O site, O(6) is bonded in a rectangular see-saw-like geometry to two equivalent La(1), one W(1), and one Ni(1) atom.