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GdB12 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Gd is bonded in a 1-coordinate geometry to twenty-four equivalent B atoms. All Gd–B bond lengths are 2.79 Å. B is bonded in a 7-coordinate geometry to two equivalent Gd and five equivalent B atoms. There is one shorter (1.73 Å) and four longer (1.79 Å) B–B bond length.
GdB2 is hexagonal omega structure structured and crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Gd is bonded to twelve equivalent B atoms to form a mixture of edge and face-sharing GdB12 cuboctahedra. All Gd–B bond lengths are 2.74 Å. B is bonded in a 9-coordinate geometry to six equivalent Gd and three equivalent B atoms. All B–B bond lengths are 1.91 Å.
Gd2OsB6 crystallizes in the orthorhombic Pbam space group. The structure is three-dimensional. there are two inequivalent Gd3+ sites. In the first Gd3+ site, Gd3+ is bonded in a 6-coordinate geometry to fourteen B2- atoms. There are a spread of Gd–B bond distances ranging from 2.77–2.85 Å. In the second Gd3+ site, Gd3+ is bonded to twelve B2- atoms to form a mixture of edge and face-sharing GdB12 cuboctahedra. There are a spread of Gd–B bond distances ranging from 2.65–2.69 Å. Os6+ is bonded in a 10-coordinate geometry to ten B2- atoms. There are a spread of Os–B bond distances ranging from 2.39–2.46 Å. There are six inequivalent B2- sites. In the first B2- site, B2- is bonded in a 3-coordinate geometry to four equivalent Gd3+, two equivalent Os6+, and three B2- atoms. There are a spread of B–B bond distances ranging from 1.77–1.85 Å. In the second B2- site, B2- is bonded in a 9-coordinate geometry to four Gd3+, two equivalent Os6+, and three B2- atoms. Both B–B bond lengths are 1.81 Å. In the third B2- site, B2- is bonded in a 9-coordinate geometry to four Gd3+, two equivalent Os6+, and three B2- atoms. There is one shorter (1.72 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 Gd3+, two equivalent Os6+, and three B2- atoms. There is one shorter (1.79 Å) and one longer (1.81 Å) B–B bond length. In the fifth B2- site, B2- is bonded in a 9-coordinate geometry to four Gd3+, two equivalent Os6+, and three B2- atoms. In the sixth B2- site, B2- is bonded in a 9-coordinate geometry to six Gd3+ and three B2- atoms. The B–B bond length is 2.18 Å.