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LiC12 crystallizes in the hexagonal P6/mmm space group. The structure is two-dimensional and consists of one LiC12 sheet oriented in the (0, 0, 1) direction. Li1+ is bonded in a cuboctahedral geometry to twelve equivalent C+0.08- atoms. All Li–C bond lengths are 2.37 Å. C+0.08- is bonded in a 4-coordinate geometry to one Li1+ and three equivalent C+0.08- atoms. All C–C bond lengths are 1.43 Å.
LiC6 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Li1+ is bonded to twelve equivalent C+0.17- atoms to form face-sharing LiC12 cuboctahedra. All Li–C bond lengths are 2.36 Å. C+0.17- is bonded in a 5-coordinate geometry to two equivalent Li1+ and three equivalent C+0.17- atoms. All C–C bond lengths are 1.44 Å.