Ni3In2S2 crystallizes in the trigonal R-3m space group. Ni(1) is bonded in a distorted linear geometry to two equivalent In(1), two equivalent In(2), and two equivalent S(1) atoms. There are two inequivalent In sites. In the first In site, In(1) is bonded to six equivalent Ni(1) and two equivalent S(1) atoms to form InNi6S2 hexagonal bipyramids that share corners with six equivalent In(1)Ni6S2 hexagonal bipyramids and faces with six equivalent In(2)Ni6S6 cuboctahedra. In the second In site, In(2) is bonded to six equivalent Ni(1) and six equivalent S(1) atoms to form distorted InNi6S6 cuboctahedra that share corners with six equivalent In(2)Ni6S6 cuboctahedra, edges with six equivalent In(2)Ni6S6 cuboctahedra, and faces with six equivalent In(1)Ni6S2 hexagonal bipyramids. S(1) is bonded in a 4-coordinate geometry to three equivalent Ni(1), one In(1), and three equivalent In(2) atoms.
Ni3In2S2 crystallizes in the trigonal R-3m space group. Ni(1) is bonded in a distorted linear geometry to two equivalent In(1), two equivalent In(2), and two equivalent S(1) atoms. Both Ni(1)-In(1) bond lengths are 2.69 Å. Both Ni(1)-In(2) bond lengths are 2.73 Å. Both Ni(1)-S(1) bond lengths are 2.15 Å. There are two inequivalent In sites. In the first In site, In(1) is bonded to six equivalent Ni(1) and two equivalent S(1) atoms to form InNi6S2 hexagonal bipyramids that share corners with six equivalent In(1)Ni6S2 hexagonal bipyramids and faces with six equivalent In(2)Ni6S6 cuboctahedra. Both In(1)-S(1) bond lengths are 3.01 Å. In the second In site, In(2) is bonded to six equivalent Ni(1) and six equivalent S(1) atoms to form distorted InNi6S6 cuboctahedra that share corners with six equivalent In(2)Ni6S6 cuboctahedra, edges with six equivalent In(2)Ni6S6 cuboctahedra, and faces with six equivalent In(1)Ni6S2 hexagonal bipyramids. All In(2)-S(1) bond lengths are 3.20 Å. S(1) is bonded in a 4-coordinate geometry to three equivalent Ni(1), one In(1), and three equivalent In(2) atoms.