Ni2V crystallizes in the orthorhombic Immm space group. V(1) is bonded to two equivalent V(1) and ten equivalent Ni(1) atoms to form VV2Ni10 cuboctahedra that share corners with two equivalent V(1)V2Ni10 cuboctahedra, corners with ten equivalent Ni(1)V5Ni7 cuboctahedra, edges with twelve equivalent V(1)V2Ni10 cuboctahedra, edges with twelve equivalent Ni(1)V5Ni7 cuboctahedra, faces with four equivalent V(1)V2Ni10 cuboctahedra, and faces with fourteen equivalent Ni(1)V5Ni7 cuboctahedra. Ni(1) is bonded to five equivalent V(1) and seven equivalent Ni(1) atoms to form NiV5Ni7 cuboctahedra that share corners with five equivalent V(1)V2Ni10 cuboctahedra, corners with seven equivalent Ni(1)V5Ni7 cuboctahedra, edges with six equivalent V(1)V2Ni10 cuboctahedra, edges with eighteen equivalent Ni(1)V5Ni7 cuboctahedra, faces with seven equivalent V(1)V2Ni10 cuboctahedra, and faces with eleven equivalent Ni(1)V5Ni7 cuboctahedra.
Ni2V crystallizes in the orthorhombic Immm space group. V(1) is bonded to two equivalent V(1) and ten equivalent Ni(1) atoms to form VV2Ni10 cuboctahedra that share corners with two equivalent V(1)V2Ni10 cuboctahedra, corners with ten equivalent Ni(1)V5Ni7 cuboctahedra, edges with twelve equivalent V(1)V2Ni10 cuboctahedra, edges with twelve equivalent Ni(1)V5Ni7 cuboctahedra, faces with four equivalent V(1)V2Ni10 cuboctahedra, and faces with fourteen equivalent Ni(1)V5Ni7 cuboctahedra. Both V(1)-V(1) bond lengths are 2.51 Å. There are two shorter (2.50 Å) and eight longer (2.51 Å) V(1)-Ni(1) bond lengths. Ni(1) is bonded to five equivalent V(1) and seven equivalent Ni(1) atoms to form NiV5Ni7 cuboctahedra that share corners with five equivalent V(1)V2Ni10 cuboctahedra, corners with seven equivalent Ni(1)V5Ni7 cuboctahedra, edges with six equivalent V(1)V2Ni10 cuboctahedra, edges with eighteen equivalent Ni(1)V5Ni7 cuboctahedra, faces with seven equivalent V(1)V2Ni10 cuboctahedra, and faces with eleven equivalent Ni(1)V5Ni7 cuboctahedra. There are a spread of Ni(1)-Ni(1) bond distances ranging from 2.49-2.54 Å.