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VCl2 is trigonal omega structured and crystallizes in the trigonal P-3m1 space group. The structure is two-dimensional and consists of one VCl2 sheet oriented in the (0, 0, 1) direction. V2+ is bonded to six equivalent Cl1- atoms to form edge-sharing VCl6 octahedra. All V–Cl bond lengths are 2.50 Å. Cl1- is bonded in a distorted T-shaped geometry to three equivalent V2+ atoms.
VCl3 is Bismuth triodide structured and crystallizes in the trigonal R-3 space group. The structure is two-dimensional and consists of three VCl3 sheets oriented in the (0, 0, 1) direction. V3+ is bonded to six equivalent Cl1- atoms to form edge-sharing VCl6 octahedra. All V–Cl bond lengths are 2.38 Å. Cl1- is bonded in an L-shaped geometry to two equivalent V3+ atoms.
VCl4 is Silicon tetrafluoride-like structured and crystallizes in the monoclinic P2/c space group. The structure is zero-dimensional and consists of four vanadium(iv) chloride molecules. V4+ is bonded in a tetrahedral geometry to four Cl1- atoms. There are three shorter (2.14 Å) and one longer (2.15 Å) V–Cl bond lengths. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom.
VCl4 is Silicon tetrafluoride-like structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of four vanadium(iv) chloride molecules. V4+ is bonded in a tetrahedral geometry to four Cl1- atoms. All V–Cl bond lengths are 2.14 Å. There are four inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one V4+ atom.