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WBr6 is Copper structured and crystallizes in the trigonal R-3 space group. The structure is zero-dimensional and consists of three hexabromotungsten molecules. W6+ is bonded in an octahedral geometry to six equivalent Br1- atoms. All W–Br bond lengths are 2.48 Å. Br1- is bonded in a single-bond geometry to one W6+ atom.
Rb2WBr6 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Rb1+ is bonded to twelve equivalent Br1- atoms to form RbBr12 cuboctahedra that share corners with twelve equivalent RbBr12 cuboctahedra, faces with six equivalent RbBr12 cuboctahedra, and faces with four equivalent WBr6 octahedra. All Rb–Br bond lengths are 3.82 Å. W4+ is bonded to six equivalent Br1- atoms to form WBr6 octahedra that share faces with eight equivalent RbBr12 cuboctahedra. All W–Br bond lengths are 2.56 Å. Br1- is bonded to four equivalent Rb1+ and one W4+ atom to form a mixture of distorted corner, edge, and face-sharing BrRb4W square pyramids.
WTeBr9 crystallizes in the monoclinic P2_1/m space group. The structure is zero-dimensional and consists of two WTeBr9 clusters. W5+ is bonded to six Br1- atoms to form WBr6 octahedra that share a faceface with one TeBr6 octahedra. There are a spread of W–Br bond distances ranging from 2.44–2.61 Å. Te4+ is bonded to six Br1- atoms to form distorted TeBr6 octahedra that share a faceface with one WBr6 octahedra. There are a spread of Te–Br bond distances ranging from 2.55–3.03 Å. There are six inequivalent Br1- sites. In the first Br1- site, Br1- is bonded in an L-shaped geometry to one W5+ and one Te4+ atom. In the second Br1- site, Br1- is bonded in a single-bond geometry to one W5+ atom. In the third Br1- site, Br1- is bonded in a single-bond geometry to one Te4+ atom. In the fourth Br1- site, Br1- is bonded in an L-shaped geometry to one W5+ and one Te4+ atom. In the fifth Br1- site, Br1- is bonded in a single-bond geometry to one W5+ atom. In the sixth Br1- site, Br1- is bonded in a single-bond geometry to one Te4+ atom.
Cs2WBr6 crystallizes in the cubic Fm-3m space group. The structure is three-dimensional. Cs1+ is bonded to twelve equivalent Br1- atoms to form CsBr12 cuboctahedra that share corners with twelve equivalent CsBr12 cuboctahedra, faces with six equivalent CsBr12 cuboctahedra, and faces with four equivalent WBr6 octahedra. All Cs–Br bond lengths are 3.94 Å. W4+ is bonded to six equivalent Br1- atoms to form WBr6 octahedra that share faces with eight equivalent CsBr12 cuboctahedra. All W–Br bond lengths are 2.56 Å. Br1- is bonded in a distorted single-bond geometry to four equivalent Cs1+ and one W4+ atom.