LiCa2NiN2 crystallizes in the orthorhombic Pmmm space group. Li(1) is bonded in a linear geometry to two equivalent N(1) atoms. Ca(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form a mixture of distorted edge and corner-sharing CaN4 tetrahedra. Ni(1) is bonded in a linear geometry to two equivalent N(2) atoms. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Li(1) and four equivalent Ca(1) atoms to form NLi2Ca4 octahedra that share corners with two equivalent N(1)Li2Ca4 octahedra, corners with eight equivalent N(2)Ca4Ni2 octahedra, and edges with two equivalent N(1)Li2Ca4 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the second N site, N(2) is bonded to four equivalent Ca(1) and two equivalent Ni(1) atoms to form NCa4Ni2 octahedra that share corners with two equivalent N(2)Ca4Ni2 octahedra, corners with eight equivalent N(1)Li2Ca4 octahedra, and edges with two equivalent N(2)Ca4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°.
LiCa2NiN2 crystallizes in the orthorhombic Pmmm space group. Li(1) is bonded in a linear geometry to two equivalent N(1) atoms. Both Li(1)-N(1) bond lengths are 1.96 Å. Ca(1) is bonded to two equivalent N(1) and two equivalent N(2) atoms to form a mixture of distorted edge and corner-sharing CaN4 tetrahedra. Both Ca(1)-N(1) bond lengths are 2.42 Å. Both Ca(1)-N(2) bond lengths are 2.59 Å. Ni(1) is bonded in a linear geometry to two equivalent N(2) atoms. Both Ni(1)-N(2) bond lengths are 1.76 Å. There are two inequivalent N sites. In the first N site, N(1) is bonded to two equivalent Li(1) and four equivalent Ca(1) atoms to form NLi2Ca4 octahedra that share corners with two equivalent N(1)Li2Ca4 octahedra, corners with eight equivalent N(2)Ca4Ni2 octahedra, and edges with two equivalent N(1)Li2Ca4 octahedra. The corner-sharing octahedral tilt angles range from 0-63°. In the second N site, N(2) is bonded to four equivalent Ca(1) and two equivalent Ni(1) atoms to form NCa4Ni2 octahedra that share corners with two equivalent N(2)Ca4Ni2 octahedra, corners with eight equivalent N(1)Li2Ca4 octahedra, and edges with two equivalent N(2)Ca4Ni2 octahedra. The corner-sharing octahedral tilt angles range from 0-63°.