The title compounds were prepared by direct reactions of the corresponding elements at high temperature. They are isostructural and crystallize in the chiral orthorhombic space group P2(1)2(1)2(1) (Li2Ce5Sn7: a = 6.273(1), b = 13.839(2), and c = 17.467(2) angstrom; Li2Pr5Sn7: a = 6.241(1), b = 13.762(2), and c = 17.367(1) angstrom; Li2Sm5Sn7: a = 6.262 (1), b = 13.809(1), and c = 17.432(1) angstrom; Li2Eu5Sn7: a = 6.165(1), b = 13.562(2), and c = 17.128(1) angstrom). The structure contains isolated Sn-7 oligomers that resemble the carbon core of an open-chain heptane molecule C7H16. Although these heptamers are stacked along the a axis at a distance that is comparable to the distances within the heptamer, electronic structure calculations show that this intermolecular contact is nonbonding for a formal charge of 16- or higher per heptamer. A hypothetical lower charge of 14-, on the other hand, leads to positive and substantial bond-overlap population that would result in branched infinite chains of (infinity)[Sn-7(14-)]. Magnetic measurements of the Ce and Pr compounds indicate a 3+ oxidation state for the rare-earth cations and, therefore, 17 available electrons from the cations per formula unit. According to four-probe conductivity measurements, the compounds are metallic.