Ca5W(N2O)2 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one N(1), two equivalent N(2), two equivalent N(3), one O(1), and one O(2) atom. In the second Ca site, Ca(2) is bonded to four equivalent N(1), one O(1), and one O(2) atom to form CaN4O2 octahedra that share corners with two equivalent W(1)N4 tetrahedra, corners with three equivalent Ca(4)N4O trigonal bipyramids, edges with two equivalent Ca(2)N4O2 octahedra, edges with four equivalent Ca(3)N2O4 octahedra,  an edgeedge with one W(1)N4 tetrahedra, and  an edgeedge with one Ca(4)N4O trigonal bipyramid. In the third Ca site, Ca(3) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form CaN2O4 octahedra that share corners with two equivalent W(1)N4 tetrahedra, edges with two equivalent Ca(3)N2O4 octahedra, edges with four equivalent Ca(2)N4O2 octahedra, and edges with two equivalent Ca(4)N4O trigonal bipyramids. In the fourth Ca site, Ca(4) is bonded to one N(2), one N(3), two equivalent N(1), and one O(1) atom to form CaN4O trigonal bipyramids that share corners with three equivalent Ca(2)N4O2 octahedra, corners with four equivalent W(1)N4 tetrahedra,  an edgeedge with one Ca(2)N4O2 octahedra, and edges with two equivalent Ca(3)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. W(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form WN4 tetrahedra that share corners with two equivalent Ca(3)N2O4 octahedra, corners with two equivalent Ca(2)N4O2 octahedra, corners with four equivalent Ca(4)N4O trigonal bipyramids, and  an edgeedge with one Ca(2)N4O2 octahedra. The corner-sharing octahedral tilt angles range from 14-74°. There are three inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), and one W(1) atom to form distorted NCa5W octahedra that share corners with three equivalent N(1)Ca5W octahedra,  a cornercorner with one O(2)Ca5 square pyramid, edges with two equivalent N(3)Ca5W octahedra, edges with three equivalent N(1)Ca5W octahedra, edges with three equivalent O(1)Ca6 octahedra, and edges with two equivalent O(2)Ca5 square pyramids. The corner-sharing octahedral tilt angles range from 0-10°. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(4), four equivalent Ca(1), and one W(1) atom. In the third N site, N(3) is bonded to one Ca(4), four equivalent Ca(1), and one W(1) atom to form NCa5W octahedra that share corners with three equivalent O(1)Ca6 octahedra, corners with two equivalent O(2)Ca5 square pyramids,  an edgeedge with one O(1)Ca6 octahedra, edges with two equivalent N(3)Ca5W octahedra, edges with four equivalent N(1)Ca5W octahedra, and  an edgeedge with one O(2)Ca5 square pyramid. The corner-sharing octahedral tilt angles range from 9-16°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Ca(2), one Ca(4), two equivalent Ca(1), and two equivalent Ca(3) atoms to form OCa6 octahedra that share corners with two equivalent O(1)Ca6 octahedra, corners with three equivalent N(3)Ca5W octahedra,  a cornercorner with one O(2)Ca5 square pyramid,  an edgeedge with one N(3)Ca5W octahedra, edges with six equivalent N(1)Ca5W octahedra, and edges with three equivalent O(2)Ca5 square pyramids. The corner-sharing octahedral tilt angles range from 0-16°. In the second O site, O(2) is bonded to one Ca(2), two equivalent Ca(1), and two equivalent Ca(3) atoms to form distorted OCa5 square pyramids that share  a cornercorner with one O(1)Ca6 octahedra, corners with two equivalent N(1)Ca5W octahedra, corners with two equivalent N(3)Ca5W octahedra, corners with two equivalent O(2)Ca5 square pyramids,  an edgeedge with one N(3)Ca5W octahedra, edges with three equivalent O(1)Ca6 octahedra, and edges with four equivalent N(1)Ca5W octahedra. The corner-sharing octahedral tilt angles range from 1-86°.
Ca5W(N2O)2 crystallizes in the monoclinic P2_1/m space group. There are four inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 7-coordinate geometry to one N(1), two equivalent N(2), two equivalent N(3), one O(1), and one O(2) atom. The Ca(1)-N(1) bond length is 2.71 Å. There is one shorter (2.60 Å) and one longer (3.00 Å) Ca(1)-N(2) bond length. There is one shorter (2.48 Å) and one longer (2.80 Å) Ca(1)-N(3) bond length. The Ca(1)-O(1) bond length is 2.36 Å. The Ca(1)-O(2) bond length is 2.45 Å. In the second Ca site, Ca(2) is bonded to four equivalent N(1), one O(1), and one O(2) atom to form CaN4O2 octahedra that share corners with two equivalent W(1)N4 tetrahedra, corners with three equivalent Ca(4)N4O trigonal bipyramids, edges with two equivalent Ca(2)N4O2 octahedra, edges with four equivalent Ca(3)N2O4 octahedra,  an edgeedge with one W(1)N4 tetrahedra, and  an edgeedge with one Ca(4)N4O trigonal bipyramid. There are two shorter (2.56 Å) and two longer (2.61 Å) Ca(2)-N(1) bond lengths. The Ca(2)-O(1) bond length is 2.48 Å. The Ca(2)-O(2) bond length is 2.24 Å. In the third Ca site, Ca(3) is bonded to two equivalent N(1), two equivalent O(1), and two equivalent O(2) atoms to form CaN2O4 octahedra that share corners with two equivalent W(1)N4 tetrahedra, edges with two equivalent Ca(3)N2O4 octahedra, edges with four equivalent Ca(2)N4O2 octahedra, and edges with two equivalent Ca(4)N4O trigonal bipyramids. Both Ca(3)-N(1) bond lengths are 2.60 Å. Both Ca(3)-O(1) bond lengths are 2.44 Å. Both Ca(3)-O(2) bond lengths are 2.35 Å. In the fourth Ca site, Ca(4) is bonded to one N(2), one N(3), two equivalent N(1), and one O(1) atom to form CaN4O trigonal bipyramids that share corners with three equivalent Ca(2)N4O2 octahedra, corners with four equivalent W(1)N4 tetrahedra,  an edgeedge with one Ca(2)N4O2 octahedra, and edges with two equivalent Ca(3)N2O4 octahedra. The corner-sharing octahedral tilt angles range from 0-15°. The Ca(4)-N(2) bond length is 2.35 Å. The Ca(4)-N(3) bond length is 2.47 Å. Both Ca(4)-N(1) bond lengths are 2.38 Å. The Ca(4)-O(1) bond length is 2.51 Å. W(1) is bonded to one N(2), one N(3), and two equivalent N(1) atoms to form WN4 tetrahedra that share corners with two equivalent Ca(3)N2O4 octahedra, corners with two equivalent Ca(2)N4O2 octahedra, corners with four equivalent Ca(4)N4O trigonal bipyramids, and  an edgeedge with one Ca(2)N4O2 octahedra. The corner-sharing octahedral tilt angles range from 14-74°. The W(1)-N(2) bond length is 1.90 Å. The W(1)-N(3) bond length is 1.89 Å. Both W(1)-N(1) bond lengths are 1.94 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded to one Ca(1), one Ca(3), one Ca(4), two equivalent Ca(2), and one W(1) atom to form distorted NCa5W octahedra that share corners with three equivalent N(1)Ca5W octahedra,  a cornercorner with one O(2)Ca5 square pyramid, edges with two equivalent N(3)Ca5W octahedra, edges with three equivalent N(1)Ca5W octahedra, edges with three equivalent O(1)Ca6 octahedra, and edges with two equivalent O(2)Ca5 square pyramids. The corner-sharing octahedral tilt angles range from 0-10°. In the second N site, N(2) is bonded in a 6-coordinate geometry to one Ca(4), four equivalent Ca(1), and one W(1) atom. In the third N site, N(3) is bonded to one Ca(4), four equivalent Ca(1), and one W(1) atom to form NCa5W octahedra that share corners with three equivalent O(1)Ca6 octahedra, corners with two equivalent O(2)Ca5 square pyramids,  an edgeedge with one O(1)Ca6 octahedra, edges with two equivalent N(3)Ca5W octahedra, edges with four equivalent N(1)Ca5W octahedra, and  an edgeedge with one O(2)Ca5 square pyramid. The corner-sharing octahedral tilt angles range from 9-16°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Ca(2), one Ca(4), two equivalent Ca(1), and two equivalent Ca(3) atoms to form OCa6 octahedra that share corners with two equivalent O(1)Ca6 octahedra, corners with three equivalent N(3)Ca5W octahedra,  a cornercorner with one O(2)Ca5 square pyramid,  an edgeedge with one N(3)Ca5W octahedra, edges with six equivalent N(1)Ca5W octahedra, and edges with three equivalent O(2)Ca5 square pyramids. The corner-sharing octahedral tilt angles range from 0-16°. In the second O site, O(2) is bonded to one Ca(2), two equivalent Ca(1), and two equivalent Ca(3) atoms to form distorted OCa5 square pyramids that share  a cornercorner with one O(1)Ca6 octahedra, corners with two equivalent N(1)Ca5W octahedra, corners with two equivalent N(3)Ca5W octahedra, corners with two equivalent O(2)Ca5 square pyramids,  an edgeedge with one N(3)Ca5W octahedra, edges with three equivalent O(1)Ca6 octahedra, and edges with four equivalent N(1)Ca5W octahedra. The corner-sharing octahedral tilt angles range from 1-86°.