Several salts (alkali, Pd(NH3)3, and iPrNH2) of 5-cyanoiminotetrazoline (C2N62-, 5-cyanoiminotetrazolinediide, CIT) were investigated. A full characterization by means of X-ray, Raman, NMR techniques, mass spectrometry, and elemental analysis is presented for the iPrNH2 (4), Cs (5), and Pd(NH3)3 (6) salts. The CIT dianion represents a nitrogen-rich binary CN dianion, and 5 forms monoclinic crystals (a = 7.345(2) Å, b = 9.505(2) Å, c = 10.198(2) Å, β = 92.12(3)°, space group P21/n, Z = 4). DSC and in situ temperature-dependent X-ray diffraction measurements of the cesium salt 5 revealed an astonishing thermal stability accompanied by a reversible phase transition from the low-temperature α modification to the metastable β modification at 253 °C. Above the melting point (334 °C), the cesium salt decomposes yielding cesium azide and cesium dicyanamide, which decomposes under further heating under release of nitrogen. The reaction of Cs2CIT with SO2 resulted in the surprising formation of a new cesium salt with the 5-cyaniminotetrazoline-1-sulfonate dianion (Cs2CITSO3·SO2 (7)). 7 crystallizes in the monoclinic space group P21 with one SO2 solvent molecule (a = 8.0080(2) Å, b = 8.0183(2) Å, c = 9.8986(3) Å, β = 108.619(1)°, Z = 2). The structure and bonding of the 10π dianion are discussed on the basis B3LYP/aug-cc-pvTZ computations (MO, NBO), and the three-dimensional array of the cesium salts with respect to the Csδ+−Nδ- in 5 compared to the Csδ+−Nδ- and Csδ+−Oδ- in 7 is discussed. Due to the expected rich bonding modes of the CIT anions, the coordination chemistry with palladium was also studied, yielding monoclinic crystals of [Pd(CIT)(NH3)3]·H2O (6, a = 7.988(2) Å, b = 8.375(2) Å, c = 13.541(3) Å, β = 104.56°, space group P21/n, Z = 4). In the solid state, the complex is composed of dimers, showing two agostic interactions and an unusual close interplanar π−π stacking of the tetrazole moiety of the CIT ligand.