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YbS2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Yb3+ is bonded in a 12-coordinate geometry to twelve equivalent S+1.50- atoms. All Yb–S bond lengths are 3.25 Å. S+1.50- is bonded to six equivalent Yb3+ and six equivalent S+1.50- atoms to form a mixture of edge, face, and corner-sharing SYb6S6 cuboctahedra. All S–S bond lengths are 2.77 Å.
YbS2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Yb3+ is bonded to eight equivalent S+1.50- atoms to form a mixture of corner and edge-sharing YbS8 hexagonal bipyramids. There are a spread of Yb–S bond distances ranging from 2.85–2.93 Å. S+1.50- is bonded in a 5-coordinate geometry to four equivalent Yb3+ and one S+1.50- atom. The S–S bond length is 2.13 Å.