Ca5Zr2N6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-coordinate geometry to one N(3), two equivalent N(1), and two equivalent N(2) atoms. In the second Ca site, Ca(2) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form distorted CaN4 trigonal pyramids that share corners with two equivalent Ca(2)N4 trigonal pyramids, corners with three equivalent Zr(1)N4 trigonal pyramids, and  an edgeedge with one Zr(1)N4 trigonal pyramid. In the third Ca site, Ca(3) is bonded in a rectangular see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. Zr(1) is bonded to one N(1), one N(2), and two equivalent N(3) atoms to form ZrN4 trigonal pyramids that share corners with three equivalent Ca(2)N4 trigonal pyramids,  an edgeedge with one Ca(2)N4 trigonal pyramid, and  an edgeedge with one Zr(1)N4 trigonal pyramid. There are three inequivalent N sites. In the first N site, N(2) is bonded in a 5-coordinate geometry to one Ca(3), two equivalent Ca(1), two equivalent Ca(2), and one Zr(1) atom. In the second N site, N(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), and two equivalent Zr(1) atoms. In the third N site, N(1) is bonded in a distorted rectangular see-saw-like geometry to one Ca(2), two equivalent Ca(1), and one Zr(1) atom.
Ca5Zr2N6 crystallizes in the monoclinic C2/c space group. There are three inequivalent Ca sites. In the first Ca site, Ca(1) is bonded in a 5-coordinate geometry to one N(3), two equivalent N(1), and two equivalent N(2) atoms. The Ca(1)-N(3) bond length is 2.84 Å. There is one shorter (2.32 Å) and one longer (2.52 Å) Ca(1)-N(1) bond length. There is one shorter (2.43 Å) and one longer (3.09 Å) Ca(1)-N(2) bond length. In the second Ca site, Ca(2) is bonded to one N(1), one N(3), and two equivalent N(2) atoms to form distorted CaN4 trigonal pyramids that share corners with two equivalent Ca(2)N4 trigonal pyramids, corners with three equivalent Zr(1)N4 trigonal pyramids, and  an edgeedge with one Zr(1)N4 trigonal pyramid. The Ca(2)-N(1) bond length is 2.36 Å. The Ca(2)-N(3) bond length is 2.54 Å. There is one shorter (2.49 Å) and one longer (2.56 Å) Ca(2)-N(2) bond length. In the third Ca site, Ca(3) is bonded in a rectangular see-saw-like geometry to two equivalent N(2) and two equivalent N(3) atoms. Both Ca(3)-N(2) bond lengths are 2.52 Å. Both Ca(3)-N(3) bond lengths are 2.43 Å. Zr(1) is bonded to one N(1), one N(2), and two equivalent N(3) atoms to form ZrN4 trigonal pyramids that share corners with three equivalent Ca(2)N4 trigonal pyramids,  an edgeedge with one Ca(2)N4 trigonal pyramid, and  an edgeedge with one Zr(1)N4 trigonal pyramid. The Zr(1)-N(1) bond length is 2.05 Å. The Zr(1)-N(2) bond length is 2.10 Å. There is one shorter (2.09 Å) and one longer (2.14 Å) Zr(1)-N(3) bond length. There are three inequivalent N sites. In the first N site, N(2) is bonded in a 5-coordinate geometry to one Ca(3), two equivalent Ca(1), two equivalent Ca(2), and one Zr(1) atom. In the second N site, N(3) is bonded in a 5-coordinate geometry to one Ca(1), one Ca(2), one Ca(3), and two equivalent Zr(1) atoms. In the third N site, N(1) is bonded in a distorted rectangular see-saw-like geometry to one Ca(2), two equivalent Ca(1), and one Zr(1) atom.