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ReTc2Si is Zincblende, Sphalerite structured and crystallizes in the orthorhombic Immm space group. The structure is zero-dimensional and consists of two rhenium molecules and two Tc2Si clusters. In each Tc2Si cluster, Tc+0.50+ is bonded in a single-bond geometry to one Si4- atom. The Tc–Si bond length is 2.31 Å. Si4- is bonded in a linear geometry to two equivalent Tc+0.50+ atoms.
ReTcSi2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two ReTcSi2 ribbons oriented in the (1, 0, 0) direction. Re3+ is bonded in a linear geometry to two equivalent Si atoms. Both Re–Si bond lengths are 2.32 Å. Tc3- is bonded in a linear geometry to two equivalent Si atoms. Both Tc–Si bond lengths are 2.31 Å. Si is bonded in a linear geometry to one Re3+ and one Tc3- atom.