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BBi is Zincblende, Sphalerite structured and crystallizes in the cubic F-43m space group. The structure is three-dimensional. B3- is bonded to four equivalent Bi3+ atoms to form corner-sharing BBi4 tetrahedra. All B–Bi bond lengths are 2.40 Å. Bi3+ is bonded to four equivalent B3- atoms to form corner-sharing BiB4 tetrahedra.
B5Bi crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of two B5Bi clusters. there are ten inequivalent B+0.60- sites. In the first B+0.60- site, B+0.60- is bonded in a 3-coordinate geometry to three B+0.60- and one Bi3+ atom. There is two shorter (1.66 Å) and one longer (1.72 Å) B–B bond length. The B–Bi bond length is 2.61 Å. In the second B+0.60- site, B+0.60- is bonded in a 3-coordinate geometry to three B+0.60- and one Bi3+ atom. There is one shorter (1.63 Å) and one longer (1.74 Å) B–B bond length. The B–Bi bond length is 2.35 Å. In the third B+0.60- site, B+0.60- is bonded in a 4-coordinate geometry to three B+0.60- and one Bi3+ atom. There is one shorter (1.64 Å) and two longer (1.69 Å) B–B bond length. The B–Bi bond length is 2.33 Å. In the fourth B+0.60- site, B+0.60- is bonded in a 4-coordinate geometry to three B+0.60- and one Bi3+ atom. There is one shorter (1.69 Å) and one longer (1.70 Å) B–B bond length. The B–Bi bond length is 2.48 Å. In the fifth B+0.60- site, B+0.60- is bonded in a 5-coordinate geometry to four B+0.60- and one Bi3+ atom. There are a spread of B–B bond distances ranging from 1.65–1.78 Å. The B–Bi bond length is 2.51 Å. In the sixth B+0.60- site, B+0.60- is bonded in a 5-coordinate geometry to five B+0.60- atoms. There is one shorter (1.58 Å) and one longer (1.74 Å) B–B bond length. In the seventh B+0.60- site, B+0.60- is bonded in a 6-coordinate geometry to five B+0.60- and one Bi3+ atom. There is one shorter (1.81 Å) and one longer (1.97 Å) B–B bond length. The B–Bi bond length is 2.55 Å. In the eighth B+0.60- site, B+0.60- is bonded in a 5-coordinate geometry to five B+0.60- atoms. There is one shorter (1.59 Å) and one longer (1.75 Å) B–B bond length. In the ninth B+0.60- site, B+0.60- is bonded in a 2-coordinate geometry to four B+0.60- and one Bi3+ atom. The B–B bond length is 1.77 Å. The B–Bi bond length is 2.45 Å. In the tenth B+0.60- site, B+0.60- is bonded in a 3-coordinate geometry to five B+0.60- atoms. There are two inequivalent Bi3+ sites. In the first Bi3+ site, Bi3+ is bonded in a distorted single-bond geometry to three B+0.60- atoms. In the second Bi3+ site, Bi3+ is bonded in a 4-coordinate geometry to four B+0.60- atoms.
B6Bi is Calcium hexaboride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. B is bonded in a 5-coordinate geometry to five equivalent B and four equivalent Bi atoms. There is one shorter (1.70 Å) and four longer (1.78 Å) B–B bond length. All B–Bi bond lengths are 3.10 Å. Bi is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms.
BBi is Wurtzite structured and crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. B3- is bonded to four equivalent Bi3+ atoms to form corner-sharing BBi4 tetrahedra. There are three shorter (2.39 Å) and one longer (2.40 Å) B–Bi bond lengths. Bi3+ is bonded to four equivalent B3- atoms to form corner-sharing BiB4 tetrahedra.