Ni2S(OF)4 crystallizes in the tetragonal P4_1 space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to one O(1), two equivalent F(1), and two equivalent F(2) atoms to form NiOF4 square pyramids that share  a cornercorner with one S(1)O4 tetrahedra and edges with two equivalent Ni(1)OF4 square pyramids. The Ni(1)-O(1) bond length is 2.06 Å. Both Ni(1)-F(1) bond lengths are 2.03 Å. There is one shorter (2.03 Å) and one longer (2.04 Å) Ni(1)-F(2) bond length. In the second Ni site, Ni(2) is bonded to one O(2), one O(3), two equivalent F(3), and two equivalent F(4) atoms to form NiO2F4 octahedra that share corners with two equivalent S(1)O4 tetrahedra and edges with two equivalent Ni(2)O2F4 octahedra. The Ni(2)-O(2) bond length is 2.04 Å. The Ni(2)-O(3) bond length is 2.10 Å. There is one shorter (1.99 Å) and one longer (2.02 Å) Ni(2)-F(3) bond length. Both Ni(2)-F(4) bond lengths are 2.03 Å. S(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SO4 tetrahedra that share corners with two equivalent Ni(2)O2F4 octahedra and  a cornercorner with one Ni(1)OF4 square pyramid. The corner-sharing octahedral tilt angles are 48°. The S(1)-O(1) bond length is 1.48 Å. The S(1)-O(2) bond length is 1.49 Å. The S(1)-O(3) bond length is 1.48 Å. The S(1)-O(4) bond length is 1.46 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Ni(1) and one S(1) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Ni(2) and one S(1) atom. In the third O site, O(3) is bonded in a distorted bent 120 degrees geometry to one Ni(2) and one S(1) atom. In the fourth O site, O(4) is bonded in a single-bond geometry to one S(1) atom. There are four inequivalent F sites. In the first F site, F(1) is bonded in a water-like geometry to two equivalent Ni(1) atoms. In the second F site, F(2) is bonded in a water-like geometry to two equivalent Ni(1) atoms. In the third F site, F(3) is bonded in an L-shaped geometry to two equivalent Ni(2) atoms. In the fourth F site, F(4) is bonded in an L-shaped geometry to two equivalent Ni(2) atoms. Linkers: 4 [O]S([O])(=O)=O. Metal clusters: 8 [Ni]. The MOF has largest included sphere 4.02 A, density 1.83 g/cm3, surface area 2851.76 m2/g, accessible volume 0.22 cm3/g