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InPb2Bi crystallizes in the orthorhombic Immm space group. The structure is one-dimensional and consists of two InPb2Bi ribbons oriented in the (1, 0, 0) direction. In is bonded in a linear geometry to two equivalent Pb atoms. Both In–Pb bond lengths are 3.25 Å. Pb is bonded in a linear geometry to one In and one Bi atom. The Pb–Bi bond length is 2.87 Å. Bi is bonded in a linear geometry to two equivalent Pb atoms.
In4PbBi3 crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. In is bonded in a 5-coordinate geometry to three equivalent In and five Bi atoms. There are one shorter (3.32 Å) and two longer (3.45 Å) In–In bond lengths. There are a spread of In–Bi bond distances ranging from 3.34–3.42 Å. Pb is bonded to six Bi atoms to form corner-sharing PbBi6 octahedra. The corner-sharing octahedra tilt angles range from 0–48°. There are four shorter (3.28 Å) and two longer (3.43 Å) Pb–Bi bond lengths. There are two inequivalent Bi sites. In the first Bi site, Bi is bonded in a 10-coordinate geometry to eight equivalent In and two equivalent Pb atoms. In the second Bi site, Bi is bonded in a 9-coordinate geometry to six equivalent In, two equivalent Pb, and one Bi atom. The Bi–Bi bond length is 3.30 Å.