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TbTe2 crystallizes in the tetragonal P4/mmm space group. The structure is zero-dimensional and consists of one TbTe2 cluster. Tb4+ is bonded in a linear geometry to two equivalent Te2- atoms. Both Tb–Te bond lengths are 3.05 Å. Te2- is bonded in a single-bond geometry to one Tb4+ atom.
Ba(TbTe2)2 crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. Ba2+ is bonded in a 8-coordinate geometry to eight Te2- atoms. There are a spread of Ba–Te bond distances ranging from 3.57–3.76 Å. There are two inequivalent Tb3+ sites. In the first Tb3+ site, Tb3+ is bonded to six Te2- atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedra tilt angles range from 47–59°. There are a spread of Tb–Te bond distances ranging from 3.07–3.15 Å. In the second Tb3+ site, Tb3+ is bonded to six Te2- atoms to form a mixture of edge and corner-sharing TbTe6 octahedra. The corner-sharing octahedra tilt angles range from 47–59°. There are a spread of Tb–Te bond distances ranging from 3.08–3.14 Å. There are four inequivalent Te2- sites. In the first Te2- site, Te2- is bonded to two equivalent Ba2+ and three Tb3+ atoms to form a mixture of distorted edge and corner-sharing TeBa2Tb3 trigonal bipyramids. In the second Te2- site, Te2- is bonded to two equivalent Ba2+ and three equivalent Tb3+ atoms to form a mixture of distorted edge and corner-sharing TeBa2Tb3 square pyramids. In the third Te2- site, Te2- is bonded in a 5-coordinate geometry to two equivalent Ba2+ and three Tb3+ atoms. In the fourth Te2- site, Te2- is bonded in a 5-coordinate geometry to two equivalent Ba2+ and three equivalent Tb3+ atoms.
TbTe2 crystallizes in the tetragonal P4/nmm space group. The structure is three-dimensional. Tb4+ is bonded in a 9-coordinate geometry to nine Te2- atoms. There are a spread of Tb–Te bond distances ranging from 3.19–3.30 Å. There are two inequivalent Te2- sites. In the first Te2- site, Te2- is bonded in a 8-coordinate geometry to four equivalent Tb4+ and four equivalent Te2- atoms. All Te–Te bond lengths are 3.15 Å. In the second Te2- site, Te2- is bonded to five equivalent Tb4+ atoms to form a mixture of distorted edge and corner-sharing TeTb5 trigonal bipyramids.
TbTe3 crystallizes in the orthorhombic Cmmm space group. The structure is two-dimensional and consists of two tellurium molecules and one TbTe2 sheet oriented in the (0, 0, 1) direction. In the TbTe2 sheet, Tb4+ is bonded in a distorted rectangular see-saw-like geometry to four equivalent Te+1.33- atoms. All Tb–Te bond lengths are 2.93 Å. Te+1.33- is bonded in a linear geometry to two equivalent Tb4+ atoms.