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Al2Cu(Ni) crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two Al2Cu(Ni) ribbons oriented in the (1, 0, 0) direction. Ni is bonded in a linear geometry to two equivalent Al atoms. Both Ni–Al bond lengths are 2.26 Å. Cu is bonded in a linear geometry to two equivalent Al atoms. Both Cu–Al bond lengths are 2.41 Å. Al is bonded in a linear geometry to one Ni and one Cu atom.
Ni6CuAl crystallizes in the tetragonal P4/mmm space group. The structure is three-dimensional. there are three inequivalent Ni sites. In the first Ni site, Ni is bonded to eight equivalent Ni and four equivalent Al atoms to form NiAl4Ni8 cuboctahedra that share corners with twelve NiAl4Ni8 cuboctahedra, edges with eight equivalent CuNi12 cuboctahedra, edges with sixteen equivalent NiAl2Cu2Ni8 cuboctahedra, faces with four equivalent AlNi12 cuboctahedra, and faces with fourteen NiAl4Ni8 cuboctahedra. All Ni–Ni bond lengths are 2.51 Å. All Ni–Al bond lengths are 2.51 Å. In the second Ni site, Ni is bonded to eight equivalent Ni and four equivalent Cu atoms to form NiCu4Ni8 cuboctahedra that share corners with twelve NiAl4Ni8 cuboctahedra, edges with eight equivalent AlNi12 cuboctahedra, edges with sixteen equivalent NiAl2Cu2Ni8 cuboctahedra, faces with four equivalent CuNi12 cuboctahedra, and faces with fourteen NiAl4Ni8 cuboctahedra. All Ni–Ni bond lengths are 2.50 Å. All Ni–Cu bond lengths are 2.51 Å. In the third Ni site, Ni is bonded to eight Ni, two equivalent Cu, and two equivalent Al atoms to form NiAl2Cu2Ni8 cuboctahedra that share corners with twelve equivalent NiAl2Cu2Ni8 cuboctahedra, edges with four equivalent CuNi12 cuboctahedra, edges with four equivalent AlNi12 cuboctahedra, edges with sixteen NiAl4Ni8 cuboctahedra, faces with two equivalent CuNi12 cuboctahedra, faces with two equivalent AlNi12 cuboctahedra, and faces with fourteen NiAl4Ni8 cuboctahedra. All Ni–Ni bond lengths are 2.51 Å. Both Ni–Cu bond lengths are 2.50 Å. Both Ni–Al bond lengths are 2.51 Å. Cu is bonded to twelve Ni atoms to form CuNi12 cuboctahedra that share corners with four equivalent CuNi12 cuboctahedra, corners with eight equivalent AlNi12 cuboctahedra, edges with twenty-four NiAl4Ni8 cuboctahedra, faces with two equivalent AlNi12 cuboctahedra, faces with four equivalent CuNi12 cuboctahedra, and faces with twelve NiCu4Ni8 cuboctahedra. Al is bonded to twelve Ni atoms to form AlNi12 cuboctahedra that share corners with four equivalent AlNi12 cuboctahedra, corners with eight equivalent CuNi12 cuboctahedra, edges with twenty-four NiCu4Ni8 cuboctahedra, faces with two equivalent CuNi12 cuboctahedra, faces with four equivalent AlNi12 cuboctahedra, and faces with twelve NiAl4Ni8 cuboctahedra.