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SiBr2 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of twenty dibromosilane molecules. Si4- is bonded in a distorted water-like geometry to two equivalent Br2+ atoms. Both Si–Br bond lengths are 2.23 Å. Br2+ is bonded in a single-bond geometry to one Si4- atom.
SiBr4 is Silicon tetrafluoride-like structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four tetrabromosilane molecules. Si4+ is bonded in a tetrahedral geometry to four Br1- atoms. All Si–Br bond lengths are 2.21 Å. There are four inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in a single-bond geometry to one Si4+ atom. In the second Br1- site, Br1- is bonded in a single-bond geometry to one Si4+ atom. In the third Br1- site, Br1- is bonded in a single-bond geometry to one Si4+ atom. In the fourth Br1- site, Br1- is bonded in a single-bond geometry to one Si4+ atom.
SiBr3 crystallizes in the monoclinic C2/m space group. The structure is zero-dimensional and consists of four tribromosilane molecules. Si is bonded in a distorted trigonal non-coplanar geometry to three Br atoms. All Si–Br bond lengths are 2.22 Å. There are two inequivalent Br sites. In the first Br site, Br is bonded in a single-bond geometry to one Si atom. In the second Br site, Br is bonded in a single-bond geometry to one Si atom.
SiBr2 crystallizes in the monoclinic C2/c space group. The structure is zero-dimensional and consists of twenty-four dibromosilane molecules. Si4- is bonded in a distorted water-like geometry to two equivalent Br2+ atoms. Both Si–Br bond lengths are 2.23 Å. Br2+ is bonded in a single-bond geometry to one Si4- atom.