LiNi2As is Cyanogen Chloride-like structured and crystallizes in the orthorhombic Immm space group. The structure is zero-dimensional and consists of two lithium molecules and two Ni2As clusters. In each Ni2As cluster, Ni1+ is bonded in a single-bond geometry to one As3- atom. The Ni–As bond length is 2.09 Å. As3- is bonded in a linear geometry to two equivalent Ni1+ atoms.
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