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V3Ga 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 Ga atoms. Both V–V bond lengths are 2.39 Å. All V–Ga bond lengths are 2.68 Å. Ga is bonded to twelve equivalent V atoms to form a mixture of edge and face-sharing GaV12 cuboctahedra.
V3Ga crystallizes in the orthorhombic Cmmm space group. The structure is three-dimensional. there are two inequivalent V sites. In the first V site, V is bonded in a 8-coordinate geometry to two equivalent V and four equivalent Ga atoms. Both V–V bond lengths are 2.59 Å. There are two shorter (2.67 Å) and two longer (3.00 Å) V–Ga bond lengths. In the second V site, V is bonded in a distorted body-centered cubic geometry to eight V atoms. All V–V bond lengths are 2.62 Å. Ga is bonded in a 12-coordinate geometry to eight equivalent V and four equivalent Ga atoms. All Ga–Ga bond lengths are 2.62 Å.