Zr4N3OF5 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one N(1), one N(2), one N(3), one O(1), one F(2), one F(4), and one F(5) atom. In the second Zr site, Zr(2) is bonded in a 8-coordinate geometry to two equivalent N(2), two equivalent N(3), one F(4), one F(5), and two equivalent F(1) atoms. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one N(1), one N(2), one N(3), one O(1), one F(3), one F(4), and one F(5) atom. In the fourth Zr site, Zr(4) is bonded in a 8-coordinate geometry to two equivalent N(1), two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms. There are three inequivalent N sites. In the first N site, N(1) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(4) atoms to form NZr4 tetrahedra that share corners with two equivalent N(2)Zr4 tetrahedra, corners with two equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(1)Zr4 tetrahedra,  an edgeedge with one N(3)Zr4 tetrahedra, and edges with two equivalent O(1)Zr4 tetrahedra. In the second N site, N(2) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(2) atoms to form NZr4 tetrahedra that share corners with two equivalent N(1)Zr4 tetrahedra, corners with two equivalent N(2)Zr4 tetrahedra,  an edgeedge with one O(1)Zr4 tetrahedra, and edges with three equivalent N(3)Zr4 tetrahedra. In the third N site, N(3) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(2) atoms to form NZr4 tetrahedra that share corners with two equivalent N(3)Zr4 tetrahedra, corners with two equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(1)Zr4 tetrahedra, and edges with three equivalent N(2)Zr4 tetrahedra. O(1) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(4) atoms to form OZr4 tetrahedra that share corners with two equivalent N(1)Zr4 tetrahedra, corners with two equivalent N(3)Zr4 tetrahedra,  an edgeedge with one N(2)Zr4 tetrahedra,  an edgeedge with one O(1)Zr4 tetrahedra, and edges with two equivalent N(1)Zr4 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Zr(2) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Zr(1) and two equivalent Zr(4) atoms. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Zr(3) and two equivalent Zr(4) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Zr(1), one Zr(2), and one Zr(3) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Zr(1), one Zr(2), and one Zr(3) atom.
Zr4N3OF5 crystallizes in the monoclinic P2_1/c space group. There are four inequivalent Zr sites. In the first Zr site, Zr(1) is bonded in a 7-coordinate geometry to one N(1), one N(2), one N(3), one O(1), one F(2), one F(4), and one F(5) atom. The Zr(1)-N(1) bond length is 2.24 Å. The Zr(1)-N(2) bond length is 2.11 Å. The Zr(1)-N(3) bond length is 2.10 Å. The Zr(1)-O(1) bond length is 2.18 Å. The Zr(1)-F(2) bond length is 2.26 Å. The Zr(1)-F(4) bond length is 2.16 Å. The Zr(1)-F(5) bond length is 2.26 Å. In the second Zr site, Zr(2) is bonded in a 8-coordinate geometry to two equivalent N(2), two equivalent N(3), one F(4), one F(5), and two equivalent F(1) atoms. There is one shorter (2.15 Å) and one longer (2.21 Å) Zr(2)-N(2) bond length. There is one shorter (2.12 Å) and one longer (2.18 Å) Zr(2)-N(3) bond length. The Zr(2)-F(4) bond length is 2.55 Å. The Zr(2)-F(5) bond length is 2.52 Å. There is one shorter (2.14 Å) and one longer (2.26 Å) Zr(2)-F(1) bond length. In the third Zr site, Zr(3) is bonded in a 7-coordinate geometry to one N(1), one N(2), one N(3), one O(1), one F(3), one F(4), and one F(5) atom. The Zr(3)-N(1) bond length is 2.13 Å. The Zr(3)-N(2) bond length is 2.11 Å. The Zr(3)-N(3) bond length is 2.12 Å. The Zr(3)-O(1) bond length is 2.29 Å. The Zr(3)-F(3) bond length is 2.24 Å. The Zr(3)-F(4) bond length is 2.31 Å. The Zr(3)-F(5) bond length is 2.14 Å. In the fourth Zr site, Zr(4) is bonded in a 8-coordinate geometry to two equivalent N(1), two equivalent O(1), two equivalent F(2), and two equivalent F(3) atoms. There is one shorter (2.06 Å) and one longer (2.16 Å) Zr(4)-N(1) bond length. There is one shorter (2.11 Å) and one longer (2.27 Å) Zr(4)-O(1) bond length. There is one shorter (2.17 Å) and one longer (2.52 Å) Zr(4)-F(2) bond length. There is one shorter (2.14 Å) and one longer (2.78 Å) Zr(4)-F(3) bond length. There are three inequivalent N sites. In the first N site, N(1) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(4) atoms to form NZr4 tetrahedra that share corners with two equivalent N(2)Zr4 tetrahedra, corners with two equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(1)Zr4 tetrahedra,  an edgeedge with one N(3)Zr4 tetrahedra, and edges with two equivalent O(1)Zr4 tetrahedra. In the second N site, N(2) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(2) atoms to form NZr4 tetrahedra that share corners with two equivalent N(1)Zr4 tetrahedra, corners with two equivalent N(2)Zr4 tetrahedra,  an edgeedge with one O(1)Zr4 tetrahedra, and edges with three equivalent N(3)Zr4 tetrahedra. In the third N site, N(3) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(2) atoms to form NZr4 tetrahedra that share corners with two equivalent N(3)Zr4 tetrahedra, corners with two equivalent O(1)Zr4 tetrahedra,  an edgeedge with one N(1)Zr4 tetrahedra, and edges with three equivalent N(2)Zr4 tetrahedra. O(1) is bonded to one Zr(1), one Zr(3), and two equivalent Zr(4) atoms to form OZr4 tetrahedra that share corners with two equivalent N(1)Zr4 tetrahedra, corners with two equivalent N(3)Zr4 tetrahedra,  an edgeedge with one N(2)Zr4 tetrahedra,  an edgeedge with one O(1)Zr4 tetrahedra, and edges with two equivalent N(1)Zr4 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded in a distorted bent 150 degrees geometry to two equivalent Zr(2) atoms. In the second F site, F(2) is bonded in a 3-coordinate geometry to one Zr(1) and two equivalent Zr(4) atoms. In the third F site, F(3) is bonded in a distorted bent 150 degrees geometry to one Zr(3) and two equivalent Zr(4) atoms. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one Zr(1), one Zr(2), and one Zr(3) atom. In the fifth F site, F(5) is bonded in a 3-coordinate geometry to one Zr(1), one Zr(2), and one Zr(3) atom.