Ni3Cl4 crystallizes in the monoclinic C2/m space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Cl(3) and four equivalent Cl(2) atoms to form edge-sharing NiCl6 octahedra. In the second Ni site, Ni(2) is bonded to one Cl(2), one Cl(4), two equivalent Cl(1), and two equivalent Cl(3) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the third Ni site, Ni(3) is bonded to three equivalent Cl(1) and three equivalent Cl(4) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. In the fourth Ni site, Ni(4) is bonded to two equivalent Cl(2) and four equivalent Cl(3) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Ni(2) and three equivalent Ni(3) atoms to form a mixture of edge and corner-sharing ClNi5 square pyramids. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Ni(2), one Ni(4), and two equivalent Ni(1) atoms. In the third Cl site, Cl(3) is bonded to one Ni(1), two equivalent Ni(2), and two equivalent Ni(4) atoms to form a mixture of edge and corner-sharing ClNi5 square pyramids. In the fourth Cl site, Cl(4) is bonded in a rectangular see-saw-like geometry to one Ni(2) and three equivalent Ni(3) atoms.
Ni3Cl4 crystallizes in the monoclinic C2/m space group. There are four inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Cl(3) and four equivalent Cl(2) atoms to form edge-sharing NiCl6 octahedra. Both Ni(1)-Cl(3) bond lengths are 2.49 Å. All Ni(1)-Cl(2) bond lengths are 2.40 Å. In the second Ni site, Ni(2) is bonded to one Cl(2), one Cl(4), two equivalent Cl(1), and two equivalent Cl(3) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. The Ni(2)-Cl(2) bond length is 2.41 Å. The Ni(2)-Cl(4) bond length is 2.40 Å. Both Ni(2)-Cl(1) bond lengths are 2.50 Å. Both Ni(2)-Cl(3) bond lengths are 2.53 Å. In the third Ni site, Ni(3) is bonded to three equivalent Cl(1) and three equivalent Cl(4) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 1-10°. There are two shorter (2.47 Å) and one longer (2.51 Å) Ni(3)-Cl(1) bond length. There are two shorter (2.39 Å) and one longer (2.49 Å) Ni(3)-Cl(4) bond length. In the fourth Ni site, Ni(4) is bonded to two equivalent Cl(2) and four equivalent Cl(3) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 2-6°. Both Ni(4)-Cl(2) bond lengths are 2.52 Å. All Ni(4)-Cl(3) bond lengths are 2.46 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to two equivalent Ni(2) and three equivalent Ni(3) atoms to form a mixture of edge and corner-sharing ClNi5 square pyramids. In the second Cl site, Cl(2) is bonded in a rectangular see-saw-like geometry to one Ni(2), one Ni(4), and two equivalent Ni(1) atoms. In the third Cl site, Cl(3) is bonded to one Ni(1), two equivalent Ni(2), and two equivalent Ni(4) atoms to form a mixture of edge and corner-sharing ClNi5 square pyramids. In the fourth Cl site, Cl(4) is bonded in a rectangular see-saw-like geometry to one Ni(2) and three equivalent Ni(3) atoms.