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WSi2 crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. W is bonded in a distorted q6 geometry to ten equivalent Si atoms. There are eight shorter (2.63 Å) and two longer (2.64 Å) W–Si bond lengths. Si is bonded in a 10-coordinate geometry to five equivalent W and five equivalent Si atoms. There are one shorter (2.60 Å) and four longer (2.65 Å) Si–Si bond lengths.
WSi2 is Titanium Disilicide-like structured and crystallizes in the hexagonal P6_222 space group. The structure is three-dimensional. W is bonded in a distorted q6 geometry to ten equivalent Si atoms. There are a spread of W–Si bond distances ranging from 2.59–2.69 Å. Si is bonded in a 10-coordinate geometry to five equivalent W and five equivalent Si atoms. There are a spread of Si–Si bond distances ranging from 2.57–2.69 Å.