Zr5N5O2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent N(1), three equivalent N(3), and one O(1) atom to form ZrN5O octahedra that share  a cornercorner with one Zr(3)N4O2 octahedra, corners with two equivalent Zr(1)N5O octahedra, and edges with five equivalent Zr(1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-60°. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to two equivalent N(3), three equivalent N(2), and two equivalent O(1) atoms. In the third Zr site, Zr(3) is bonded to four equivalent N(2) and two equivalent O(1) atoms to form ZrN4O2 octahedra that share corners with two equivalent Zr(1)N5O octahedra and edges with two equivalent Zr(3)N4O2 octahedra. The corner-sharing octahedral tilt angles are 60°. There are three inequivalent N sites. In the first N site, N(1) is bonded in a square co-planar geometry to four equivalent Zr(1) atoms. In the second N site, N(2) is bonded to two equivalent Zr(3) and three equivalent Zr(2) atoms to form distorted NZr5 trigonal bipyramids that share corners with four equivalent O(1)Zr4 tetrahedra, corners with two equivalent N(2)Zr5 trigonal bipyramids, corners with four equivalent N(3)Zr5 trigonal bipyramids, edges with three equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with five equivalent N(2)Zr5 trigonal bipyramids. In the third N site, N(3) is bonded to two equivalent Zr(2) and three equivalent Zr(1) atoms to form NZr5 trigonal bipyramids that share corners with five equivalent O(1)Zr4 tetrahedra, corners with four equivalent N(2)Zr5 trigonal bipyramids,  an edgeedge with one O(1)Zr4 tetrahedra,  an edgeedge with one N(2)Zr5 trigonal bipyramid, and edges with four equivalent N(3)Zr5 trigonal bipyramids. O(1) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(2) atoms to form OZr4 tetrahedra that share corners with three equivalent O(1)Zr4 tetrahedra, corners with four equivalent N(2)Zr5 trigonal bipyramids, corners with five equivalent N(3)Zr5 trigonal bipyramids,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with three equivalent N(2)Zr5 trigonal bipyramids.
Zr5N5O2 crystallizes in the monoclinic C2/m space group. There are three inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to two equivalent N(1), three equivalent N(3), and one O(1) atom to form ZrN5O octahedra that share  a cornercorner with one Zr(3)N4O2 octahedra, corners with two equivalent Zr(1)N5O octahedra, and edges with five equivalent Zr(1)N5O octahedra. The corner-sharing octahedral tilt angles range from 0-60°. Both Zr(1)-N(1) bond lengths are 2.21 Å. All Zr(1)-N(3) bond lengths are 2.25 Å. The Zr(1)-O(1) bond length is 2.20 Å. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to two equivalent N(3), three equivalent N(2), and two equivalent O(1) atoms. Both Zr(2)-N(3) bond lengths are 2.34 Å. There are two shorter (2.32 Å) and one longer (2.45 Å) Zr(2)-N(2) bond length. Both Zr(2)-O(1) bond lengths are 2.25 Å. In the third Zr site, Zr(3) is bonded to four equivalent N(2) and two equivalent O(1) atoms to form ZrN4O2 octahedra that share corners with two equivalent Zr(1)N5O octahedra and edges with two equivalent Zr(3)N4O2 octahedra. The corner-sharing octahedral tilt angles are 60°. All Zr(3)-N(2) bond lengths are 2.23 Å. Both Zr(3)-O(1) bond lengths are 2.15 Å. There are three inequivalent N sites. In the first N site, N(1) is bonded in a square co-planar geometry to four equivalent Zr(1) atoms. In the second N site, N(2) is bonded to two equivalent Zr(3) and three equivalent Zr(2) atoms to form distorted NZr5 trigonal bipyramids that share corners with four equivalent O(1)Zr4 tetrahedra, corners with two equivalent N(2)Zr5 trigonal bipyramids, corners with four equivalent N(3)Zr5 trigonal bipyramids, edges with three equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with five equivalent N(2)Zr5 trigonal bipyramids. In the third N site, N(3) is bonded to two equivalent Zr(2) and three equivalent Zr(1) atoms to form NZr5 trigonal bipyramids that share corners with five equivalent O(1)Zr4 tetrahedra, corners with four equivalent N(2)Zr5 trigonal bipyramids,  an edgeedge with one O(1)Zr4 tetrahedra,  an edgeedge with one N(2)Zr5 trigonal bipyramid, and edges with four equivalent N(3)Zr5 trigonal bipyramids. O(1) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(2) atoms to form OZr4 tetrahedra that share corners with three equivalent O(1)Zr4 tetrahedra, corners with four equivalent N(2)Zr5 trigonal bipyramids, corners with five equivalent N(3)Zr5 trigonal bipyramids,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with three equivalent N(2)Zr5 trigonal bipyramids.