Five new isotypic quaternary chalcogenides containing rare-earth metal atoms crystallizing in the hexagonal noncentrosymmetric space group P6(3) (No. 173) with the La(3)CuSiS(7) structure type have been synthesized by reacting the appropriate anhydrous rare-earth trichloride with sodium thiogermanate, Na(2)GeS(3). The reaction between LnCl(3) and Na(2)GeS(3) in an evacuated fused-silica ampule produced high yields of good-quality crystals of NaLn(3)GeS(7) [Ln = Ce (I), Nd (II), Sm (III), Gd (IV), and Yb (V)], while a similar reaction between EuCl(3) and Na(2)GeS(3) yielded a quinary chloride thiogermanate, Na(1.2)Eu(3.4)Cl(2)Ge(3)S(9) (VI), incorporating a cyclic trimeric Ge(3)S(9) building unit and adopting a structure related to La(3)CuSiS(7). The crystal structure of the compounds comprises a complex network of bicapped trigonal-prismatic LnS(8) and GeS(4) tetrahedra, which creates channels along the [001] direction. The Na(+) cations reside in these channels within trigonally distorted octahedral coordination environments, surrounded by six S atoms. For compounds III-V, the temperature dependence of the magnetic susceptibility indicates that these compounds are paramagnetic with μ(eff). = 1.86, 8.01, and 3.87 μ(B), for III-V, respectively. The experimental μ(eff) for IV is close to the theoretical value of 7.94 for free Gd(3+) ions, while μ(eff) values for III and V deviate from their theoretical values of 0.86 and 4.54 μ(B) for Sm(3+) and Yb(3+) ions, respectively. These compounds are semiconductors with optical band gaps of around 1.3 eV for III and V. Extended Hückel calculations suggest that the valence band comprises primarily S 3p and the bottom of the conduction band is dominated by empty rare-earth 5d orbitals. Compound VI exhibits a sharp optical absorption of around 2.18 eV, which is attributed to the f → d transition of Eu(II). The effective magnetic moment of 7.94 μ(B)/Eu is in excellent agreement with the theoretical value of 7.94 μ(B) for the free Eu(2+) ion.