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The stannides  RE  3 Rh 2 Sn 4  ( RE  = Y, Gd–Tm, Lu) were synthesized from the elements by arc-melting and subsequent annealing (1220 K for  RE  = Y, Gd–Tm and 1170 K for  RE  = Lu) in sealed silica ampoules for 11 days. X-ray powder diffraction studies confirm the hexagonal Lu 3 Co 2 In 4  type structure, space groupP6   ‾$P\overline{6}$. The structure of Gd 3 Rh 2 Sn 4  was refined from single crystal X-ray diffractometer data for a twinned crystal:  a  = 744.04(6),  c  = 409.23(4) pm,  wR 2 = 0.0288, 567  F  2  values and 21 variables. The  RE  3 Rh 2 Sn 4  stannides derive from the well-known equiatomic stannides  RE RhSn (≍ RE  3 Rh 3 Sn 3 ) by Rh/Sn ordering within the  RE  6  trigonal prisms. The striking structural motif is the trigonal planar tin coordination of the Sn2 atoms with 288 pm Sn2–Sn1 distances. The Sn2 atoms carry substantially more negative charge than the Sn1 atoms. This is underlined by  119 Sn isomer shifts of  δ  = 1.86(1) mm s −1  for Sn1 and  δ  = 2.26(1) mm s −1  for Sn2 detected in the Mössbauer spectrum of Lu 3 Rh 2 Sn 4 . From atoms in molecules (AIM) analysis of the charge density obtained with calculation based on density functional theory (DFT) for Y 3 Rh 2 Sn 4 , the charge transfer proceeds from yttrium towards more electronegative rhodium. Little departure from neutrality is observed for tin whose itinerant  s -like states are little involved with the bonding. The site projected density of states (DOS) and the crystal orbital overlap population (COOP) plots further illustrate these observations and reveal major Y–Rh and Rh–Sn bonding, while Y–Sn bonding is weaker.

RE 3 Rh 2 Sn 4 ( RE = Y, Gd–Tm, Lu) – first stannides with Lu 3 Co 2 In 4 type structure