The reaction of CsN₃ with GaS and S at elevated temperatures results in Cs₂Ga₂S₅. Its crystal structure was determined from single-crystal X-ray diffraction data. The colorless solid crystallizes in space group C2/c (no. 15) with V=1073.3(4) ų and Z=4. Cs₂Ga₂S₅ is the first compound that features one-dimensional chains [Ga₂S₃(S₂)²⁻] of edge- and corner-sharing GaS₄ tetrahedra. The vibrational band of the S₂²⁻ units at 493 cm⁻¹ was revealed by Raman spectroscopy. Cs₂Ga₂S₅ has a wide bandgap of about 3.26 eV. The thermal decomposition of CsN₃ yields elemental Cs, which reacts with sulfur to provide Cs₂S₆ as an intermediate product. The crystal structure of Cs₂S₆ was redetermined from selected single crystals. The red compound crystallizes in space group with V=488.99(8) ų and Z=2. Cs₂S₆ consists of S₆²⁻ polysulfide chains and two Cs positions with coordination numbers of 10 and 11, respectively. Results of DFT calculations on Cs₂Ga₂S₅ are in good agreement with the experimental crystal structure and Raman data. The analysis of the chemical bonding behavior revealed completely ionic bonds for Cs, whereas GaS and SS form polarized and fully covalent bonds, respectively. HOMO and LUMO are centered at the S₂ units.

Li₁₇Sb₁₃S₂₈ was synthesized by solid-state reaction of stoichiometric amounts of anhydrous Li₂S and Sb₂S₃. The crystal structure of Li₁₇Sb₁₃S₂₈ was determined from dark-red single crystals at room temperature. The title compound crystallizes in the monoclinic space group C2/m (no. 12) with a=12.765(2) Å, b=11.6195(8) Å, c=9.2564(9) Å, β=119.665(6)°, V=1193.0(2) ų, and Z=4 (data at 20 °C, lattice constants from powder diffraction). The crystal structure contains one cation site with a mixed occupation by Li and Sb, and one with an antimony split position. Antimony and sulfur form slightly distorted tetragonal bipyramidal [SbS₅E] units (E=free electron pair). Six of these units are arranged around a vacancy in the anion substructure. The lone electron pairs E of the antimony(III) cations are arranged around these vacancies. Thus, a variant of the rock salt structure type with ordered vacancies in the anionic substructure results. Impedance spectroscopic measurements of Li₁₇Sb₁₃S₂₈ show a specific conductivity of 2.9×10⁻⁹ Ω⁻¹ cm⁻¹ at 323 K and of 7.9×10⁻⁶ Ω⁻¹ cm⁻¹ at 563 K, the corresponding activation energy is E_A=0.4 eV below 403 K and E_A=0.6 eV above. Raman spectra are dominated by the SbS stretching modes of the [SbS₅] units at 315 and 341 cm⁻¹ at room temperature. Differential thermal analysis (DTA) measurements of Li₁₇Sb₁₃S₂₈ indicate peritectic melting at 854 K.

Phosphorus sulfide cages α-P₄S₄, α-P₄S₅, β-P₄S₅, and β-P₄S₆ and transition-metal chlorides TaCl₅ and NbCl₅ form molecular adducts in CS₂/n-hexane. The crystal structures of the adducts (TaCl₅)(α-P₄S₄), (TaCl₅)(α-P₄S₅), (TaCl₅)(β-P₄S₅), (NbCl₅)(β-P₄S₅), and (TaCl₅)(β-P₄S₆) are reported and their conformation and energetic stability are discussed on the basis of ab initio electronic structure calculations. Furthermore bond lengths of coordinated and noncoordinated phosphorus sulfide cages obtained from experiment and theory are compared, emphasizing the changes within the cages that emerge upon coordination.