Lithium dimethylcuprate exists as a dimer in diethyl ether forming an 8-membered ring. Similarly, lithium diphenylcuprate crystallizes as a dimeric etherate, .
If the Li ions is complexed with the crown ether 12-crown-4, the resulting diorganylcuprate anions adopt a linear coordination geometry at copper.
For the higher order cyanocuprate LiCuCN(CH), the cyanide ligand is coordinated to Li and π-bound to Cu.