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GdB6 is Calcium hexaboride structured and crystallizes in the cubic Pm-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 3.02 Å. B is bonded in a 1-coordinate geometry to four equivalent Gd and five equivalent B atoms. There is one shorter (1.64 Å) and four longer (1.75 Å) B–B bond length.
Gd2B5 crystallizes in the monoclinic P2_1/c space group. The structure is three-dimensional. there are two inequivalent Gd sites. In the first Gd site, Gd is bonded in a 12-coordinate geometry to twelve B atoms. There are a spread of Gd–B bond distances ranging from 2.62–2.90 Å. In the second Gd site, Gd is bonded in a 12-coordinate geometry to twelve B atoms. There are a spread of Gd–B bond distances ranging from 2.64–3.05 Å. There are five inequivalent B sites. In the first B site, B is bonded in a 9-coordinate geometry to four Gd and five B atoms. There are a spread of B–B bond distances ranging from 1.67–1.83 Å. In the second B site, B is bonded in a 8-coordinate geometry to six Gd and two B atoms. The B–B bond length is 1.66 Å. In the third B site, B is bonded in a 9-coordinate geometry to four Gd and five B atoms. There is one shorter (1.73 Å) and two longer (1.80 Å) B–B bond length. In the fourth B site, B is bonded in a 3-coordinate geometry to six Gd and three B atoms. There is one shorter (1.74 Å) and one longer (1.82 Å) B–B bond length. In the fifth B site, B is bonded in a 9-coordinate geometry to four Gd and five B atoms.
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.
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.