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V3Sb crystallizes in the cubic Pm-3n space group. The structure is three-dimensional. V is bonded in a 6-coordinate geometry to two equivalent V and four equivalent Sb atoms. Both V–V bond lengths are 2.47 Å. All V–Sb bond lengths are 2.76 Å. Sb is bonded to twelve equivalent V atoms to form a mixture of edge and face-sharing SbV12 cuboctahedra.
VSb2 is Khatyrkite structured and crystallizes in the tetragonal I4/mcm space group. The structure is three-dimensional. V5+ is bonded in a 8-coordinate geometry to eight equivalent Sb+2.50- atoms. All V–Sb bond lengths are 2.86 Å. Sb+2.50- is bonded in a 4-coordinate geometry to four equivalent V5+ atoms.
V3Sb2 crystallizes in the trigonal R-3m space group. The structure is three-dimensional. V2+ is bonded to five Sb3- atoms to form a mixture of distorted edge, face, and corner-sharing VSb5 trigonal bipyramids. There are a spread of V–Sb bond distances ranging from 2.76–2.85 Å. There are two inequivalent Sb3- sites. In the first Sb3- site, Sb3- is bonded in a distorted q6 geometry to nine equivalent V2+ atoms. In the second Sb3- site, Sb3- is bonded in a 6-coordinate geometry to six equivalent V2+ atoms.
V5Sb4 is Titanium telluride structured and crystallizes in the tetragonal I4/m space group. The structure is three-dimensional. there are two inequivalent V+2.40+ sites. In the first V+2.40+ site, V+2.40+ is bonded in a square co-planar geometry to four equivalent Sb3- atoms. All V–Sb bond lengths are 2.94 Å. In the second V+2.40+ site, V+2.40+ is bonded to five equivalent Sb3- atoms to form a mixture of corner and edge-sharing VSb5 square pyramids. There are a spread of V–Sb bond distances ranging from 2.68–2.72 Å. Sb3- is bonded in a 6-coordinate geometry to six V+2.40+ atoms.