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HfMo2 crystallizes in the orthorhombic Fmmm space group. The structure is one-dimensional and consists of four HfMo2 ribbons oriented in the (1, 0, 0) direction. Hf is bonded in a 4-coordinate geometry to four equivalent Mo atoms. All Hf–Mo bond lengths are 2.87 Å. Mo is bonded in a 4-coordinate geometry to two equivalent Hf atoms.
HfMo2 is Cubic Laves structured and crystallizes in the cubic Fd-3m space group. The structure is three-dimensional. Hf is bonded in a 12-coordinate geometry to twelve equivalent Mo atoms. All Hf–Mo bond lengths are 3.14 Å. Mo is bonded to six equivalent Hf and six equivalent Mo atoms to form a mixture of edge, corner, and face-sharing MoHf6Mo6 cuboctahedra. All Mo–Mo bond lengths are 2.68 Å.
HfMo2 is Cubic Laves-like structured and crystallizes in the hexagonal P6_3/mmc space group. The structure is three-dimensional. there are two inequivalent Hf sites. In the first Hf site, Hf is bonded in a 12-coordinate geometry to twelve Mo atoms. There are three shorter (3.11 Å) and nine longer (3.15 Å) Hf–Mo bond lengths. In the second Hf site, Hf is bonded in a 12-coordinate geometry to twelve Mo atoms. There are a spread of Hf–Mo bond distances ranging from 3.14–3.16 Å. There are three inequivalent Mo sites. In the first Mo site, Mo is bonded to six Hf and six Mo atoms to form a mixture of corner, edge, and face-sharing MoHf6Mo6 cuboctahedra. There are three shorter (2.66 Å) and three longer (2.71 Å) Mo–Mo bond lengths. In the second Mo site, Mo is bonded to six Hf and six Mo atoms to form a mixture of corner, edge, and face-sharing MoHf6Mo6 cuboctahedra. All Mo–Mo bond lengths are 2.69 Å. In the third Mo site, Mo is bonded to six Hf and six Mo atoms to form a mixture of corner, edge, and face-sharing MoHf6Mo6 cuboctahedra. There are two shorter (2.64 Å) and two longer (2.74 Å) Mo–Mo bond lengths.