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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.
Yb5Si4 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are three inequivalent Yb sites. In the first Yb site, Yb is bonded in a 6-coordinate geometry to six Si atoms. There are a spread of Yb–Si bond distances ranging from 2.97–3.12 Å. In the second Yb site, Yb is bonded to six Si atoms to form a mixture of distorted corner, edge, and face-sharing YbSi6 octahedra. The corner-sharing octahedra tilt angles range from 38–47°. There are a spread of Yb–Si bond distances ranging from 3.10–3.26 Å. In the third Yb site, Yb is bonded to six Si atoms to form a mixture of distorted corner and face-sharing YbSi6 octahedra. The corner-sharing octahedra tilt angles range from 45–60°. There are a spread of Yb–Si bond distances ranging from 3.01–3.34 Å. There are three inequivalent Si sites. In the first Si site, Si is bonded in a 9-coordinate geometry to eight Yb and one Si atom. The Si–Si bond length is 2.37 Å. In the second Si site, Si is bonded in a 8-coordinate geometry to seven Yb and one Si atom. The Si–Si bond length is 2.38 Å. In the third Si site, Si is bonded in a 9-coordinate geometry to eight Yb and one Si atom.
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.
Yb3Si is beta Cu3Ti-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. Yb is bonded in a 4-coordinate geometry to four equivalent Si atoms. There are two shorter (3.23 Å) and two longer (3.40 Å) Yb–Si bond lengths. Si is bonded to twelve equivalent Yb atoms to form a mixture of corner and face-sharing SiYb12 cuboctahedra.