The first structural reports of anhydrous salts containing the CS2N3 moiety are presented. The new M+CS2N3-species (M = NH4 (1), (CH3)(4)N (2), Cs (3), K (4)) were characterized by vibrational spectroscopy (IR, Raman), as well as multinuclear NMR spectroscopy (H-1, C-13, N-14 NMR). Moreover, the solid-state structures of NH4CS2N3 (1) [orthorhombic, Pbca, a = 10.6787(1) Angstrom, b = 6.8762(1) Angstrom, c = 15.2174(2) Angstrom, V = 1117.40(2) Angstrom(3), Z = 8] and (H3C)(4)NCS2N3 (2) [monoclinic, P2(1)/m, a = 5.9011(1) Angstrom, b = 7.3565(2) Angstrom, c = 10.9474(3) Angstrom, beta = 91.428(1)degrees, V = 475.09(2) Angstrom(3), Z = 2] were determined using X-ray diffraction techniques. The covalent compound CH3CS2N3 (5) was prepared by the reaction of methyl iodide with sodium azidodithiocarbonate and was characterized by vibrational spectroscopy (IR, Raman), multinuclear NMR spectroscopy (H-1, C-13, N-14), and X-ray diffraction techniques [monoclinic, P2(1)/m, a = 5.544(1) Angstrom, b = 6.4792(7) Angstrom, c = 7.629(1) Angstrom, beta = 105.53(2)degrees, V = 264.06(7) Angstrom(3), Z = 2]. Furthermore, the gas-phase structure of 5 was calculated (MPW1PW91/cc-pVTZ) and found to be in very good agreement with the experimentally determined structure. Improved synthetic routes for the recently reported dipseudohalogen (CS2N3)(2) and interpseudohalogen CS2N3CN (6) are described, and the calculated gas-phase structure of 6 was compared with the experimentally determined structure (X-ray). The vibrational spectra of 6 and HCS2N3 (7) are also reported. Furthermore, several plausible isomers for 7 were calculated in an attempt to rationalize the experimentally observed structure which has N-H and not S-H connectivity. The lowest energy isomer for 7 is in agreement with the experimentally observed structure, and the Bronsted acidity was calculated at the MPW1PW91/cc-pVTZ level of theory. The unknown CSe2N3- anion (8) was also investigated both theoretically and experimentally, and the structure and vibrational data for the unknown CTe2N3- anion (9) were investigated by quantum-chemical calculations using a quasi-relativistic pseudopotential for Te (ECP46MWB) and a cc-pVTZ basis set for C and N. The gas-phase structure of 9 is predicted to be that of a five-membered ring in analogy to the sulfur and selenium analogues.