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Rb3Ge crystallizes in the hexagonal P6_3/mmc space group. The structure is one-dimensional and consists of two Rb3Ge ribbons oriented in the (0, 0, 1) direction. Rb is bonded in a distorted water-like geometry to two equivalent Ge atoms. Both Rb–Ge bond lengths are 3.90 Å. Ge is bonded in a 6-coordinate geometry to six equivalent Rb atoms.
Rb3Ge is alpha bismuth trifluoride structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. there are two inequivalent Rb sites. In the first Rb site, Rb is bonded to four equivalent Rb and four equivalent Ge atoms to form a mixture of distorted edge, face, and corner-sharing RbRb4Ge4 tetrahedra. All Rb–Rb bond lengths are 3.95 Å. All Rb–Ge bond lengths are 3.95 Å. In the second Rb site, Rb is bonded in a body-centered cubic geometry to eight equivalent Rb atoms. Ge is bonded in a body-centered cubic geometry to eight equivalent Rb atoms.