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TbB12 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Tb is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All Tb–B bond lengths are 2.79 Å. B is bonded in a 7-coordinate geometry to two equivalent Tb and five equivalent B atoms. There is one shorter (1.72 Å) and four longer (1.79 Å) B–B bond length.
TbB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Tb is bonded to twelve equivalent B atoms to form a mixture of edge and face-sharing TbB12 cuboctahedra. All Tb–B bond lengths are 2.73 Å. B is bonded in a 9-coordinate geometry to six equivalent Tb and three equivalent B atoms. All B–B bond lengths are 1.91 Å.
Tb2RuB6 crystallizes in the orthorhombic Pbam space group. The structure is three-dimensional. there are two inequivalent Tb3+ sites. In the first Tb3+ site, Tb3+ is bonded in a 6-coordinate geometry to fourteen B2- atoms. There are a spread of Tb–B bond distances ranging from 2.74–2.82 Å. In the second Tb3+ site, Tb3+ is bonded to twelve B2- atoms to form a mixture of edge and face-sharing TbB12 cuboctahedra. There are a spread of Tb–B bond distances ranging from 2.62–2.65 Å. Ru6+ is bonded in a 10-coordinate geometry to ten B2- atoms. There are a spread of Ru–B bond distances ranging from 2.35–2.42 Å. There are six inequivalent B2- sites. In the first B2- site, B2- is bonded in a 9-coordinate geometry to four equivalent Tb3+, two equivalent Ru6+, and three B2- atoms. There are a spread of B–B bond distances ranging from 1.78–1.85 Å. In the second B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Ru6+, and three B2- atoms. There is one shorter (1.81 Å) and one longer (1.82 Å) B–B bond length. In the third B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Ru6+, and three B2- atoms. There is one shorter (1.73 Å) and one longer (1.89 Å) B–B bond length. In the fourth B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Ru6+, and three B2- atoms. Both B–B bond lengths are 1.79 Å. In the fifth B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Ru6+, and three B2- atoms. In the sixth B2- site, B2- is bonded in a 9-coordinate geometry to six Tb3+ and three B2- atoms. The B–B bond length is 2.18 Å.
Tb2ReB6 crystallizes in the orthorhombic Pbam space group. The structure is three-dimensional. there are two inequivalent Tb3+ sites. In the first Tb3+ site, Tb3+ is bonded in a 4-coordinate geometry to fourteen B2- atoms. There are a spread of Tb–B bond distances ranging from 2.76–2.83 Å. In the second Tb3+ site, Tb3+ is bonded to twelve B2- atoms to form a mixture of edge and face-sharing TbB12 cuboctahedra. There are a spread of Tb–B bond distances ranging from 2.61–2.65 Å. Re6+ is bonded in a 10-coordinate geometry to ten B2- atoms. There are a spread of Re–B bond distances ranging from 2.36–2.42 Å. There are six inequivalent B2- sites. In the first B2- site, B2- is bonded in a 9-coordinate geometry to six Tb3+ and three B2- atoms. There are a spread of B–B bond distances ranging from 1.85–2.02 Å. In the second B2- site, B2- is bonded in a 9-coordinate geometry to four equivalent Tb3+, two equivalent Re6+, and three B2- atoms. There are a spread of B–B bond distances ranging from 1.80–1.85 Å. In the third B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Re6+, and three B2- atoms. The B–B bond length is 1.82 Å. In the fourth B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Re6+, and three B2- atoms. There is one shorter (1.74 Å) and one longer (1.87 Å) B–B bond length. In the fifth B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Re6+, and three B2- atoms. The B–B bond length is 1.80 Å. In the sixth B2- site, B2- is bonded in a 9-coordinate geometry to four Tb3+, two equivalent Re6+, and three B2- atoms.