Benzene has played an important role in the development of the ideas concerning ′aromaticity′, as much as that benzene and its derivatives are the best examples of aromatic compounds. Although the inorganic aromatic compounds have been found to obey Hückel 4n+2 π electron rule, they often possess a different number of πe as compared to their organic analogues. One such system is cyclic compounds of S3N3, where 10 π aromatic S3N3− and 8π S3N3+ are known, but interestingly, a 6π benzene‐analogue of the sulfur‐nitrogen compound is not reported. Hence as a case study, we have undertaken an extensive theoretical investigation of the electronic structure of 6π, 8π and 10π electrons cyclic S3N33+, S3N3+ and S3N3−, based on the Energy Decomposition Analysis (EDA). We have also compared the results with isoelectronic classical C6H6, C6H62− and C6H64−. Our results indicated that the π‐contribution increases and the σ‐contribution decreases, while the contribution from the orbital interaction energy remains nearly similar upon addition of π electrons to C6H6 and S3N33+. However, the major decrease in the interaction energy is caused by the drastic reduction of the electrostatic component in C6H64− and S3N33+, which can be correlated to the instability of these molecules. Thus, aromatic binary compounds of sulfur and nitrogen are commonly π‐electron rich, while their aromatic hydrocarbon analogues are π‐electron precise.
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