Zr5N5O2 crystallizes in the monoclinic Cm space group. There are five inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one N(4), two equivalent N(1), two equivalent N(3), and one O(2) atom to form ZrN5O octahedra that share  a cornercorner with one Zr(5)N4O2 octahedra, corners with two equivalent Zr(4)N5O octahedra, edges with two equivalent Zr(1)N5O octahedra, and edges with three equivalent Zr(4)N5O octahedra. The corner-sharing octahedral tilt angles range from 3-60°. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to one N(2), two equivalent N(4), two equivalent N(5), and two equivalent O(1) atoms. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one N(5), two equivalent N(2), two equivalent N(3), and two equivalent O(2) atoms. In the fourth Zr site, Zr(4) is bonded to one N(3), two equivalent N(1), two equivalent N(4), and one O(1) atom to form ZrN5O octahedra that share  a cornercorner with one Zr(5)N4O2 octahedra, corners with two equivalent Zr(1)N5O octahedra, edges with two equivalent Zr(4)N5O octahedra, and edges with three equivalent Zr(1)N5O octahedra. The corner-sharing octahedral tilt angles range from 3-59°. In the fifth Zr site, Zr(5) is bonded to two equivalent N(2), two equivalent N(5), one O(1), and one O(2) atom to form ZrN4O2 octahedra that share  a cornercorner with one Zr(1)N5O octahedra,  a cornercorner with one Zr(4)N5O octahedra, and edges with two equivalent Zr(5)N4O2 octahedra. The corner-sharing octahedral tilt angles range from 59-60°. There are five inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1) and two equivalent Zr(4) atoms. In the second N site, N(2) is bonded to one Zr(2), two equivalent Zr(3), and two equivalent Zr(5) atoms to form distorted NZr5 square pyramids that share corners with four equivalent O(2)Zr4 tetrahedra, corners with two equivalent N(3)Zr5 trigonal bipyramids, corners with two equivalent N(4)Zr5 trigonal bipyramids, corners with two equivalent N(5)Zr5 trigonal bipyramids, edges with two equivalent N(2)Zr5 square pyramids,  an edgeedge with one O(2)Zr4 tetrahedra, edges with two equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with three equivalent N(5)Zr5 trigonal bipyramids. In the third N site, N(3) is bonded to one Zr(4), two equivalent Zr(1), and two equivalent Zr(3) atoms to form NZr5 trigonal bipyramids that share corners with two equivalent N(2)Zr5 square pyramids,  a cornercorner with one O(1)Zr4 tetrahedra, corners with four equivalent O(2)Zr4 tetrahedra, corners with two equivalent N(5)Zr5 trigonal bipyramids,  an edgeedge with one N(2)Zr5 square pyramid,  an edgeedge with one O(2)Zr4 tetrahedra, edges with two equivalent N(3)Zr5 trigonal bipyramids, and edges with two equivalent N(4)Zr5 trigonal bipyramids. In the fourth N site, N(4) is bonded to one Zr(1), two equivalent Zr(2), and two equivalent Zr(4) atoms to form NZr5 trigonal bipyramids that share corners with two equivalent N(2)Zr5 square pyramids,  a cornercorner with one O(2)Zr4 tetrahedra, corners with four equivalent O(1)Zr4 tetrahedra, corners with two equivalent N(5)Zr5 trigonal bipyramids,  an edgeedge with one O(1)Zr4 tetrahedra,  an edgeedge with one N(5)Zr5 trigonal bipyramid, edges with two equivalent N(3)Zr5 trigonal bipyramids, and edges with two equivalent N(4)Zr5 trigonal bipyramids. In the fifth N site, N(5) is bonded to one Zr(3), two equivalent Zr(2), and two equivalent Zr(5) atoms to form distorted NZr5 trigonal bipyramids that share corners with two equivalent N(2)Zr5 square pyramids, corners with four equivalent O(1)Zr4 tetrahedra, corners with two equivalent N(3)Zr5 trigonal bipyramids, corners with two equivalent N(4)Zr5 trigonal bipyramids, edges with three equivalent N(2)Zr5 square pyramids,  an edgeedge with one O(1)Zr4 tetrahedra, edges with two equivalent O(2)Zr4 tetrahedra,  an edgeedge with one N(4)Zr5 trigonal bipyramid, and edges with two equivalent N(5)Zr5 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Zr(4), one Zr(5), and two equivalent Zr(2) atoms to form OZr4 tetrahedra that share  a cornercorner with one O(2)Zr4 tetrahedra, corners with two equivalent O(1)Zr4 tetrahedra,  a cornercorner with one N(3)Zr5 trigonal bipyramid, corners with four equivalent N(4)Zr5 trigonal bipyramids, corners with four equivalent N(5)Zr5 trigonal bipyramids, edges with two equivalent N(2)Zr5 square pyramids,  an edgeedge with one N(4)Zr5 trigonal bipyramid, and  an edgeedge with one N(5)Zr5 trigonal bipyramid. In the second O site, O(2) is bonded to one Zr(1), one Zr(5), and two equivalent Zr(3) atoms to form OZr4 tetrahedra that share corners with four equivalent N(2)Zr5 square pyramids,  a cornercorner with one O(1)Zr4 tetrahedra, corners with two equivalent O(2)Zr4 tetrahedra,  a cornercorner with one N(4)Zr5 trigonal bipyramid, corners with four equivalent N(3)Zr5 trigonal bipyramids,  an edgeedge with one N(2)Zr5 square pyramid,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with two equivalent N(5)Zr5 trigonal bipyramids.
Zr5N5O2 crystallizes in the monoclinic Cm space group. There are five inequivalent Zr sites. In the first Zr site, Zr(1) is bonded to one N(4), two equivalent N(1), two equivalent N(3), and one O(2) atom to form ZrN5O octahedra that share  a cornercorner with one Zr(5)N4O2 octahedra, corners with two equivalent Zr(4)N5O octahedra, edges with two equivalent Zr(1)N5O octahedra, and edges with three equivalent Zr(4)N5O octahedra. The corner-sharing octahedral tilt angles range from 3-60°. The Zr(1)-N(4) bond length is 2.25 Å. Both Zr(1)-N(1) bond lengths are 2.19 Å. Both Zr(1)-N(3) bond lengths are 2.25 Å. The Zr(1)-O(2) bond length is 2.22 Å. In the second Zr site, Zr(2) is bonded in a 7-coordinate geometry to one N(2), two equivalent N(4), two equivalent N(5), and two equivalent O(1) atoms. The Zr(2)-N(2) bond length is 2.47 Å. Both Zr(2)-N(4) bond lengths are 2.36 Å. Both Zr(2)-N(5) bond lengths are 2.30 Å. Both Zr(2)-O(1) bond lengths are 2.24 Å. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one N(5), two equivalent N(2), two equivalent N(3), and two equivalent O(2) atoms. The Zr(3)-N(5) bond length is 2.43 Å. Both Zr(3)-N(2) bond lengths are 2.28 Å. Both Zr(3)-N(3) bond lengths are 2.36 Å. Both Zr(3)-O(2) bond lengths are 2.26 Å. In the fourth Zr site, Zr(4) is bonded to one N(3), two equivalent N(1), two equivalent N(4), and one O(1) atom to form ZrN5O octahedra that share  a cornercorner with one Zr(5)N4O2 octahedra, corners with two equivalent Zr(1)N5O octahedra, edges with two equivalent Zr(4)N5O octahedra, and edges with three equivalent Zr(1)N5O octahedra. The corner-sharing octahedral tilt angles range from 3-59°. The Zr(4)-N(3) bond length is 2.26 Å. Both Zr(4)-N(1) bond lengths are 2.20 Å. Both Zr(4)-N(4) bond lengths are 2.24 Å. The Zr(4)-O(1) bond length is 2.19 Å. In the fifth Zr site, Zr(5) is bonded to two equivalent N(2), two equivalent N(5), one O(1), and one O(2) atom to form ZrN4O2 octahedra that share  a cornercorner with one Zr(1)N5O octahedra,  a cornercorner with one Zr(4)N5O octahedra, and edges with two equivalent Zr(5)N4O2 octahedra. The corner-sharing octahedral tilt angles range from 59-60°. Both Zr(5)-N(2) bond lengths are 2.23 Å. Both Zr(5)-N(5) bond lengths are 2.24 Å. The Zr(5)-O(1) bond length is 2.15 Å. The Zr(5)-O(2) bond length is 2.15 Å. There are five inequivalent N sites. In the first N site, N(1) is bonded in a rectangular see-saw-like geometry to two equivalent Zr(1) and two equivalent Zr(4) atoms. In the second N site, N(2) is bonded to one Zr(2), two equivalent Zr(3), and two equivalent Zr(5) atoms to form distorted NZr5 square pyramids that share corners with four equivalent O(2)Zr4 tetrahedra, corners with two equivalent N(3)Zr5 trigonal bipyramids, corners with two equivalent N(4)Zr5 trigonal bipyramids, corners with two equivalent N(5)Zr5 trigonal bipyramids, edges with two equivalent N(2)Zr5 square pyramids,  an edgeedge with one O(2)Zr4 tetrahedra, edges with two equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with three equivalent N(5)Zr5 trigonal bipyramids. In the third N site, N(3) is bonded to one Zr(4), two equivalent Zr(1), and two equivalent Zr(3) atoms to form NZr5 trigonal bipyramids that share corners with two equivalent N(2)Zr5 square pyramids,  a cornercorner with one O(1)Zr4 tetrahedra, corners with four equivalent O(2)Zr4 tetrahedra, corners with two equivalent N(5)Zr5 trigonal bipyramids,  an edgeedge with one N(2)Zr5 square pyramid,  an edgeedge with one O(2)Zr4 tetrahedra, edges with two equivalent N(3)Zr5 trigonal bipyramids, and edges with two equivalent N(4)Zr5 trigonal bipyramids. In the fourth N site, N(4) is bonded to one Zr(1), two equivalent Zr(2), and two equivalent Zr(4) atoms to form NZr5 trigonal bipyramids that share corners with two equivalent N(2)Zr5 square pyramids,  a cornercorner with one O(2)Zr4 tetrahedra, corners with four equivalent O(1)Zr4 tetrahedra, corners with two equivalent N(5)Zr5 trigonal bipyramids,  an edgeedge with one O(1)Zr4 tetrahedra,  an edgeedge with one N(5)Zr5 trigonal bipyramid, edges with two equivalent N(3)Zr5 trigonal bipyramids, and edges with two equivalent N(4)Zr5 trigonal bipyramids. In the fifth N site, N(5) is bonded to one Zr(3), two equivalent Zr(2), and two equivalent Zr(5) atoms to form distorted NZr5 trigonal bipyramids that share corners with two equivalent N(2)Zr5 square pyramids, corners with four equivalent O(1)Zr4 tetrahedra, corners with two equivalent N(3)Zr5 trigonal bipyramids, corners with two equivalent N(4)Zr5 trigonal bipyramids, edges with three equivalent N(2)Zr5 square pyramids,  an edgeedge with one O(1)Zr4 tetrahedra, edges with two equivalent O(2)Zr4 tetrahedra,  an edgeedge with one N(4)Zr5 trigonal bipyramid, and edges with two equivalent N(5)Zr5 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Zr(4), one Zr(5), and two equivalent Zr(2) atoms to form OZr4 tetrahedra that share  a cornercorner with one O(2)Zr4 tetrahedra, corners with two equivalent O(1)Zr4 tetrahedra,  a cornercorner with one N(3)Zr5 trigonal bipyramid, corners with four equivalent N(4)Zr5 trigonal bipyramids, corners with four equivalent N(5)Zr5 trigonal bipyramids, edges with two equivalent N(2)Zr5 square pyramids,  an edgeedge with one N(4)Zr5 trigonal bipyramid, and  an edgeedge with one N(5)Zr5 trigonal bipyramid. In the second O site, O(2) is bonded to one Zr(1), one Zr(5), and two equivalent Zr(3) atoms to form OZr4 tetrahedra that share corners with four equivalent N(2)Zr5 square pyramids,  a cornercorner with one O(1)Zr4 tetrahedra, corners with two equivalent O(2)Zr4 tetrahedra,  a cornercorner with one N(4)Zr5 trigonal bipyramid, corners with four equivalent N(3)Zr5 trigonal bipyramids,  an edgeedge with one N(2)Zr5 square pyramid,  an edgeedge with one N(3)Zr5 trigonal bipyramid, and edges with two equivalent N(5)Zr5 trigonal bipyramids.