Crystal structure of N-(1,3-benzothiazol-2-yl)-4-iodobenzene-1-sulfonohydrazide: the unexpected importance of l N-H—π and I—π interactions on the supramolecular arrangement

Authors: Gomes, L. R.; Früchtl, H.; Low, J. N.; MOURIK, T.; Pinheiro, A. C.; De Souza, M. V. N.; Wardell, J. L.
Source: Zeitschrift für anorganische und allgemeine Chemie (ZAAC), v. e, p. 1-9, 2022
Publisher: ZAAC

Abstract

The 2-hydrazinyl-1,3-benzothiazole derivatives are precursors for synthesis of several compounds of technological interest, including the Bt−NH−N=CHR₁ (R₁=alkyl, aryl, heteroaryl), derivatives. Usually when Bt−NH−NH₂ is allowed to react with a benzenesulfonyl chloride the substitution is observed in the terminal nitrogen of the arenehydrazine unit, but when 4-iodophenyl sulfonyl chloride (4-IC₆H₄SO₂Cl) was used, the product isolated was the title compound as confirmed by Rx-analysis. Determination of the crystal structure revealed that the definition of the arrangement was driven by N−H⋅⋅⋅π, C−I⋅⋅⋅π and S2−O21⋅⋅⋅π interactions instead of the classic O⋅⋅⋅H−N hydrogen bonds. The interactions were confirmed by HS analysis. Interaction energy calculations showed that the π interactions-based motifs play an important role in the supramolecular arrangement, contributing about 60 % to the total energy of the lattice. DFT calculations showed that the energy of the C−I⋅⋅⋅π dimer is complemented with contributions of π⋅⋅⋅π stacking and N−H⋅⋅⋅π interaction between the primary amine and the thiazole aromatic ring.

Keywords: sulfonohydrazide, benzotiazole, iodobenzene, π-interactions, intermolecular forces
Document Type: Research Article
DOI: 10.1002/zaac.202200087
Publication date: 1 de setembro de 2022