Ni5Cl6 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles are 13°. In the second Ni site, Ni(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the third Ni site, Ni(3) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Ni(1), two equivalent Ni(2), and two 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 to one Ni(1), two equivalent Ni(2), and two equivalent Ni(3) atoms to form a mixture of edge and corner-sharing ClNi5 square pyramids.
Ni5Cl6 crystallizes in the monoclinic C2/m space group. There are three inequivalent Ni sites. In the first Ni site, Ni(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles are 13°. Both Ni(1)-Cl(2) bond lengths are 2.45 Å. All Ni(1)-Cl(1) bond lengths are 2.45 Å. In the second Ni site, Ni(2) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Ni(2)-Cl(2) bond lengths are 2.36 Å. There are two shorter (2.34 Å) and two longer (2.81 Å) Ni(2)-Cl(1) bond lengths. In the third Ni site, Ni(3) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form a mixture of edge and corner-sharing NiCl6 octahedra. The corner-sharing octahedral tilt angles range from 5-13°. Both Ni(3)-Cl(2) bond lengths are 2.61 Å. There are two shorter (2.33 Å) and two longer (2.47 Å) Ni(3)-Cl(1) bond lengths. There are two inequivalent Cl sites. In the first Cl site, Cl(1) is bonded to one Ni(1), two equivalent Ni(2), and two 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 to one Ni(1), two equivalent Ni(2), and two equivalent Ni(3) atoms to form a mixture of edge and corner-sharing ClNi5 square pyramids.