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VMoTc2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two VMoTc2 ribbons oriented in the (1, 0, 0) direction. V4+ is bonded in a linear geometry to two equivalent Tc3- atoms. Both V–Tc bond lengths are 2.12 Å. Mo2+ is bonded in a linear geometry to two equivalent Tc3- atoms. Both Mo–Tc bond lengths are 2.25 Å. Tc3- is bonded in a linear geometry to one V4+ and one Mo2+ atom.
V2MoTc crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two V2MoTc ribbons oriented in the (1, 0, 0) direction. V is bonded in a linear geometry to one Mo and one Tc atom. The V–Mo bond length is 2.18 Å. The V–Tc bond length is 2.17 Å. Mo is bonded in a linear geometry to two equivalent V atoms. Tc is bonded in a linear geometry to two equivalent V atoms.