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TiSi2 is Titanium Disilicide structured and crystallizes in the orthorhombic Fddd space group. The structure is three-dimensional. Ti is bonded in a 10-coordinate geometry to ten equivalent Si atoms. There are a spread of Ti–Si bond distances ranging from 2.56–2.78 Å. Si is bonded in a 10-coordinate geometry to five equivalent Ti and five equivalent Si atoms. There are a spread of Si–Si bond distances ranging from 2.54–2.80 Å.
TiSi2 crystallizes in the orthorhombic Immm space group. The structure is three-dimensional. Ti is bonded in a 10-coordinate geometry to ten equivalent Si atoms. There are eight shorter (2.67 Å) and two longer (2.78 Å) Ti–Si bond lengths. Si is bonded in a 9-coordinate geometry to five equivalent Ti and four equivalent Si atoms. All Si–Si bond lengths are 2.63 Å.
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TiSi2(OCl)2(Si(CH3)3)4Si(CH3)2 crystallizes in the monoclinic P2_1 space group. The structure is zero-dimensional and consists of two dimethylsilane molecules, eight trimethylsilyl radical molecules, and two TiSi2(OCl)2 clusters. In each TiSi2(OCl)2 cluster, Ti2+ is bonded in a tetrahedral geometry to two O2- and two Cl1- atoms. Both Ti–O bond lengths are 1.77 Å. There are one shorter (2.25 Å) and one longer (2.26 Å) Ti–Cl bond lengths. There are two inequivalent Si+2.86+ sites. In the first Si+2.86+ site, Si+2.86+ is bonded in a single-bond geometry to one O2- atom. The Si–O bond length is 1.72 Å. In the second Si+2.86+ site, Si+2.86+ is bonded in a single-bond geometry to one O2- atom. The Si–O bond length is 1.72 Å. There are two inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti2+ and one Si+2.86+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti2+ and one Si+2.86+ atom. There are two inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Ti2+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Ti2+ atom.