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HfTiNi2 crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two HfTiNi2 ribbons oriented in the (1, 0, 0) direction. Hf is bonded in a linear geometry to two equivalent Ni atoms. Both Hf–Ni bond lengths are 2.19 Å. Ti is bonded in a linear geometry to two equivalent Ni atoms. Both Ti–Ni bond lengths are 2.52 Å. Ni is bonded in a linear geometry to one Hf and one Ti atom.
Hf2TiNi3 crystallizes in the orthorhombic Fddd space group. The structure is three-dimensional. there are three inequivalent Hf sites. In the first Hf site, Hf is bonded in a body-centered cubic geometry to eight Ni atoms. There are a spread of Hf–Ni bond distances ranging from 2.66–2.73 Å. In the second Hf site, Hf is bonded in a 9-coordinate geometry to one Ti and eight Ni atoms. The Hf–Ti bond length is 2.78 Å. There are a spread of Hf–Ni bond distances ranging from 2.56–2.77 Å. In the third Hf site, Hf is bonded in a 9-coordinate geometry to one Ti and eight Ni atoms. The Hf–Ti bond length is 2.86 Å. There are a spread of Hf–Ni bond distances ranging from 2.58–2.98 Å. There are three inequivalent Ti sites. In the first Ti site, Ti is bonded in a 6-coordinate geometry to six Hf and eight Ni atoms. There are four shorter (2.99 Å) and four longer (3.12 Å) Ti–Ni bond lengths. In the second Ti site, Ti is bonded in a distorted cuboctahedral geometry to eight Ni atoms. There are four shorter (2.59 Å) and four longer (2.70 Å) Ti–Ni bond lengths. In the third Ti site, Ti is bonded in a distorted body-centered cubic geometry to eight Ni atoms. There are a spread of Ti–Ni bond distances ranging from 2.51–2.71 Å. There are three inequivalent Ni sites. In the first Ni site, Ni is bonded in a 8-coordinate geometry to five Hf and three Ti atoms. In the second Ni site, Ni is bonded in a 8-coordinate geometry to six Hf and two Ti atoms. In the third Ni site, Ni is bonded in a 7-coordinate geometry to five Hf and three Ti atoms.