Ni3OF5 is Hydrophilite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form NiOF5 octahedra that share corners with three equivalent Ni(4)O2F4 octahedra, corners with five equivalent Ni(2)OF5 octahedra,  an edgeedge with one Ni(3)F6 octahedra, and  an edgeedge with one Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the second Ni site, Ni(2) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(3) atoms to form NiOF5 octahedra that share corners with three equivalent Ni(3)F6 octahedra, corners with five equivalent Ni(1)OF5 octahedra,  an edgeedge with one Ni(4)O2F4 octahedra, and  an edgeedge with one Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. In the third Ni site, Ni(3) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NiF6 octahedra that share corners with two equivalent Ni(4)O2F4 octahedra, corners with six equivalent Ni(2)OF5 octahedra, and edges with two equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(4) atoms to form NiO2F4 octahedra that share corners with two equivalent Ni(3)F6 octahedra, corners with six equivalent Ni(1)OF5 octahedra, and edges with two equivalent Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles are 50°. O(1) is bonded in a trigonal planar geometry to one Ni(1), one Ni(2), and one Ni(4) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one Ni(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ni(2), one Ni(3), and one Ni(4) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Ni(1) and two equivalent Ni(2) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Ni(4) and two equivalent Ni(1) atoms.
Ni3OF5 is Hydrophilite-derived structured and crystallizes in the monoclinic C2/m space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), one F(3), two equivalent F(1), and two equivalent F(4) atoms to form NiOF5 octahedra that share corners with three equivalent Ni(4)O2F4 octahedra, corners with five equivalent Ni(2)OF5 octahedra,  an edgeedge with one Ni(3)F6 octahedra, and  an edgeedge with one Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Ni(1)-O(1) bond length is 1.94 Å. The Ni(1)-F(3) bond length is 2.05 Å. Both Ni(1)-F(1) bond lengths are 2.03 Å. Both Ni(1)-F(4) bond lengths are 2.04 Å. In the second Ni site, Ni(2) is bonded to one O(1), one F(2), two equivalent F(1), and two equivalent F(3) atoms to form NiOF5 octahedra that share corners with three equivalent Ni(3)F6 octahedra, corners with five equivalent Ni(1)OF5 octahedra,  an edgeedge with one Ni(4)O2F4 octahedra, and  an edgeedge with one Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-52°. The Ni(2)-O(1) bond length is 1.97 Å. The Ni(2)-F(2) bond length is 2.03 Å. Both Ni(2)-F(1) bond lengths are 2.03 Å. There is one shorter (2.04 Å) and one longer (2.06 Å) Ni(2)-F(3) bond length. In the third Ni site, Ni(3) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form NiF6 octahedra that share corners with two equivalent Ni(4)O2F4 octahedra, corners with six equivalent Ni(2)OF5 octahedra, and edges with two equivalent Ni(1)OF5 octahedra. The corner-sharing octahedral tilt angles range from 48-50°. Both Ni(3)-F(2) bond lengths are 1.99 Å. All Ni(3)-F(1) bond lengths are 2.03 Å. In the fourth Ni site, Ni(4) is bonded to two equivalent O(1), two equivalent F(2), and two equivalent F(4) atoms to form NiO2F4 octahedra that share corners with two equivalent Ni(3)F6 octahedra, corners with six equivalent Ni(1)OF5 octahedra, and edges with two equivalent Ni(2)OF5 octahedra. The corner-sharing octahedral tilt angles are 50°. Both Ni(4)-O(1) bond lengths are 1.99 Å. Both Ni(4)-F(2) bond lengths are 2.03 Å. Both Ni(4)-F(4) bond lengths are 2.05 Å. O(1) is bonded in a trigonal planar geometry to one Ni(1), one Ni(2), and one Ni(4) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Ni(1), one Ni(2), and one Ni(3) atom. In the second F site, F(2) is bonded in a distorted trigonal planar geometry to one Ni(2), one Ni(3), and one Ni(4) atom. In the third F site, F(3) is bonded in a trigonal planar geometry to one Ni(1) and two equivalent Ni(2) atoms. In the fourth F site, F(4) is bonded in a trigonal planar geometry to one Ni(4) and two equivalent Ni(1) atoms.