CaNi2S5 crystallizes in the orthorhombic Pmmn space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. Ni(1) is bonded to one S(1), one S(3), and three equivalent S(2) atoms to form a mixture of corner and edge-sharing NiS5 trigonal bipyramids. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1) and two equivalent Ni(1) atoms to form corner-sharing SCa2Ni2 tetrahedra. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Ca(1) and three equivalent Ni(1) atoms. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Ni(1), and one S(3) atom.
CaNi2S5 crystallizes in the orthorhombic Pmmn space group. Ca(1) is bonded in a 8-coordinate geometry to two equivalent S(1), two equivalent S(2), and four equivalent S(3) atoms. Both Ca(1)-S(1) bond lengths are 2.77 Å. Both Ca(1)-S(2) bond lengths are 3.11 Å. All Ca(1)-S(3) bond lengths are 2.86 Å. Ni(1) is bonded to one S(1), one S(3), and three equivalent S(2) atoms to form a mixture of corner and edge-sharing NiS5 trigonal bipyramids. The Ni(1)-S(1) bond length is 2.20 Å. The Ni(1)-S(3) bond length is 2.26 Å. There is one shorter (2.20 Å) and two longer (2.27 Å) Ni(1)-S(2) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded to two equivalent Ca(1) and two equivalent Ni(1) atoms to form corner-sharing SCa2Ni2 tetrahedra. In the second S site, S(2) is bonded in a 4-coordinate geometry to one Ca(1) and three equivalent Ni(1) atoms. In the third S site, S(3) is bonded in a 4-coordinate geometry to two equivalent Ca(1), one Ni(1), and one S(3) atom. The S(3)-S(3) bond length is 2.10 Å.