Ca3(WN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-coordinate geometry to two equivalent N(1) and three equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. There are two inequivalent W sites. In the first W site, W(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. In the second W site, W(2) is bonded in a distorted see-saw-like geometry to two equivalent N(1) and two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), two equivalent Ca(1), one W(1), and one W(2) atom to form distorted NCa3W2 trigonal bipyramids that share corners with six equivalent N(2)Ca4W2 octahedra, corners with three equivalent N(1)Ca3W2 trigonal bipyramids, edges with three equivalent N(2)Ca4W2 octahedra, and  an edgeedge with one N(1)Ca3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-68°. In the second N site, N(2) is bonded to one Ca(2), three equivalent Ca(1), one W(1), and one W(2) atom to form NCa4W2 octahedra that share corners with four equivalent N(2)Ca4W2 octahedra, corners with six equivalent N(1)Ca3W2 trigonal bipyramids,  an edgeedge with one N(2)Ca4W2 octahedra, edges with three equivalent N(1)Ca3W2 trigonal bipyramids, and  a faceface with one N(2)Ca4W2 octahedra. The corner-sharing octahedral tilt angles range from 27-66°.
Ca3(WN2)2 crystallizes in the orthorhombic Pnna space group. There are two inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-coordinate geometry to two equivalent N(1) and three equivalent N(2) atoms. There is one shorter (2.59 Å) and one longer (2.82 Å) Ca(1)-N(1) bond length. There are a spread of Ca(1)-N(2) bond distances ranging from 2.46-2.57 Å. In the second Ca site, Ca(2) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both Ca(2)-N(1) bond lengths are 2.53 Å. Both Ca(2)-N(2) bond lengths are 2.71 Å. There are two inequivalent W sites. In the first W site, W(1) is bonded in a 4-coordinate geometry to two equivalent N(1) and two equivalent N(2) atoms. Both W(1)-N(1) bond lengths are 2.03 Å. Both W(1)-N(2) bond lengths are 2.00 Å. In the second W site, W(2) is bonded in a distorted see-saw-like geometry to two equivalent N(1) and two equivalent N(2) atoms. Both W(2)-N(1) bond lengths are 1.99 Å. Both W(2)-N(2) bond lengths are 2.08 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to one Ca(2), two equivalent Ca(1), one W(1), and one W(2) atom to form distorted NCa3W2 trigonal bipyramids that share corners with six equivalent N(2)Ca4W2 octahedra, corners with three equivalent N(1)Ca3W2 trigonal bipyramids, edges with three equivalent N(2)Ca4W2 octahedra, and  an edgeedge with one N(1)Ca3W2 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 22-68°. In the second N site, N(2) is bonded to one Ca(2), three equivalent Ca(1), one W(1), and one W(2) atom to form NCa4W2 octahedra that share corners with four equivalent N(2)Ca4W2 octahedra, corners with six equivalent N(1)Ca3W2 trigonal bipyramids,  an edgeedge with one N(2)Ca4W2 octahedra, edges with three equivalent N(1)Ca3W2 trigonal bipyramids, and  a faceface with one N(2)Ca4W2 octahedra. The corner-sharing octahedral tilt angles range from 27-66°.