Ni3Cl4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form a mixture of corner and edge-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. In the second Ni site, Ni(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form edge-sharing NiCl6 octahedra. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to one Ni(2) and four equivalent Ni(1) atoms to form a mixture of corner and edge-sharing ClNi5 square pyramids. In the second Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1) and two equivalent Ni(2) atoms.
Ni3Cl4 crystallizes in the orthorhombic Cmmm space group. There are two inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Cl(1) and four equivalent Cl(2) atoms to form a mixture of corner and edge-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 0-5°. Both Ni(1)-Cl(1) bond lengths are 2.44 Å. All Ni(1)-Cl(2) bond lengths are 2.49 Å. In the second Ni site, Ni(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form edge-sharing NiCl6 octahedra. Both Ni(2)-Cl(2) bond lengths are 2.45 Å. All Ni(2)-Cl(1) bond lengths are 2.42 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to one Ni(2) and four equivalent Ni(1) atoms to form a mixture of corner and edge-sharing ClNi5 square pyramids. In the second Cl site, Cl(1) is bonded in a rectangular see-saw-like geometry to two equivalent Ni(1) and two equivalent Ni(2) atoms.