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YbSi crystallizes in the orthorhombic Cmcm space group. The structure is three-dimensional. Yb is bonded in a 7-coordinate geometry to seven equivalent Si atoms. There are a spread of Yb–Si bond distances ranging from 3.08–3.16 Å. Si is bonded in a 9-coordinate geometry to seven equivalent Yb and two equivalent Si atoms. Both Si–Si bond lengths are 2.44 Å.
YbSi2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Yb is bonded to twelve equivalent Si atoms to form a mixture of face and edge-sharing YbSi12 cuboctahedra. All Yb–Si bond lengths are 3.13 Å. Si is bonded in a 9-coordinate geometry to six equivalent Yb and three equivalent Si atoms. All Si–Si bond lengths are 2.35 Å.
Yb3Si5 crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. Yb is bonded in a 10-coordinate geometry to ten Si atoms. There are a spread of Yb–Si bond distances ranging from 3.10–3.20 Å. There are two inequivalent Si sites. In the first Si site, Si is bonded in a 9-coordinate geometry to six equivalent Yb and three equivalent Si atoms. All Si–Si bond lengths are 2.36 Å. In the second Si site, Si is bonded in a 8-coordinate geometry to six equivalent Yb and two equivalent Si atoms.