Metal-doped nitrogen clusters serve as effective models for elucidating the geometries and electronic properties of nitrogen-rich compounds at the molecular scale. Herein, we have conducted a systematic study of VIB-group metal chromium (Cr) doped nitrogen clusters through a combination of mass spectrometry techniques and density functional theory (DFT) calculations. The laser ablation is employed to generate CrNn+ clusters. The results reveal that CrN8+ clusters exhibited the highest signal intensity in mass spectrometry. The photodissociation experiments with 266 nm photons confirm that the chromium heteroazide clusters are composed of chromium ions and nitrogen molecules. Further structural searches and electronic properties calculations of chromium-nitrogen clusters indicate that the cationic CrN8+ cluster is an X-shaped geometry with D2 symmetry exhibiting robust stability. Molecular orbital and chemical bond analyses demonstrate the existence of strong interactions between Cr+ cation and N2 ligands. The present findings enrich the geometries of metal doped nitrogen clusters and provide valuable guidance for the rational design and synthesis of novel transition metal nitrides.