Molecular beam electric deflection experiments on neutral single copper-doped tin clusters are presented at different cryogenic nozzle temperatures. The experimental cluster beam profiles SnNCu (N = 9–16) are compared with classical rotational dynamic simulations of globally optimized structures obtained by a genetic algorithm based on density functional theory. The formation of endohedral complexes with comparable geometry to manganese- and gold-doped tin is confirmed. Theoretical methods predict ionic structures of the type Cuδ−@SnNδ+ with electron transfer from the tin cage to the central copper dopant. This behaviour is discussed based on a molecular orbital picture particularly with respect to other transition metal tetrel complexes.