NaNiH4SO6F crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(3), two equivalent O(1), two equivalent O(4), and one F(1) atom to form distorted NaO5F pentagonal pyramids that share corners with two equivalent Ni(1)O4F2 octahedra, corners with three equivalent S(1)O4 tetrahedra, and edges with two equivalent Ni(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 66°. Ni(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form NiO4F2 octahedra that share corners with two equivalent Ni(1)O4F2 octahedra, corners with two equivalent Na(1)O5F pentagonal pyramids, corners with two equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(1)O5F pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. S(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SO4 tetrahedra that share corners with two equivalent Ni(1)O4F2 octahedra and corners with three equivalent Na(1)O5F pentagonal pyramids. The corner-sharing octahedral tilt angles are 54°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one Na(1), one Ni(1), one H(1), and one H(2) atom. F(1) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Ni(1) atoms.
NaNiH4SO6F crystallizes in the monoclinic P2_1/m space group. Na(1) is bonded to one O(3), two equivalent O(1), two equivalent O(4), and one F(1) atom to form distorted NaO5F pentagonal pyramids that share corners with two equivalent Ni(1)O4F2 octahedra, corners with three equivalent S(1)O4 tetrahedra, and edges with two equivalent Ni(1)O4F2 octahedra. The corner-sharing octahedral tilt angles are 66°. The Na(1)-O(3) bond length is 2.35 Å. Both Na(1)-O(1) bond lengths are 2.65 Å. Both Na(1)-O(4) bond lengths are 2.45 Å. The Na(1)-F(1) bond length is 2.24 Å. Ni(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form NiO4F2 octahedra that share corners with two equivalent Ni(1)O4F2 octahedra, corners with two equivalent Na(1)O5F pentagonal pyramids, corners with two equivalent S(1)O4 tetrahedra, and edges with two equivalent Na(1)O5F pentagonal pyramids. The corner-sharing octahedral tilt angles are 48°. Both Ni(1)-O(1) bond lengths are 2.11 Å. Both Ni(1)-O(4) bond lengths are 2.09 Å. Both Ni(1)-F(1) bond lengths are 2.00 Å. There are two inequivalent H sites. In the first H site, H(1) is bonded in a single-bond geometry to one O(4) atom. The H(1)-O(4) bond length is 0.99 Å. In the second H site, H(2) is bonded in a single-bond geometry to one O(4) atom. The H(2)-O(4) bond length is 0.99 Å. S(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SO4 tetrahedra that share corners with two equivalent Ni(1)O4F2 octahedra and corners with three equivalent Na(1)O5F pentagonal pyramids. The corner-sharing octahedral tilt angles are 54°. The S(1)-O(2) bond length is 1.52 Å. The S(1)-O(3) bond length is 1.46 Å. Both S(1)-O(1) bond lengths are 1.50 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Na(1), one Ni(1), and one S(1) atom. In the second O site, O(2) is bonded in a single-bond geometry to one S(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Na(1) and one S(1) atom. In the fourth O site, O(4) is bonded in a distorted water-like geometry to one Na(1), one Ni(1), one H(1), and one H(2) atom. F(1) is bonded in a trigonal planar geometry to one Na(1) and two equivalent Ni(1) atoms.