Expected and unexpected products of reactions of 2-hydrazinylbenzo-thia-zole with 3-nitro-benzene-sulfonyl chloride in different solvents.

Alexandra Morscher,James L Wardell,Marcus V N De Souza,William T A Harrison

doi:10.1107/s2056989018005595

Alexandra Morscher, James L Wardell + Show 2 more

Open Access

https://doi.org/10.1107/s2056989018005595

Copy DOI

Abstract

The syntheses and crystal structures of 2-[2-(propan-2-yl-idene)hydrazin-yl]-1,3-benzo-thia-zol-3-ium 3-nitro-benzene-sulfonate (C10H12N2S+·C6H4NO5S-), (I), 2-[2-(3-nitro-benzene-sulfon-yl)hydrazin-yl]-1,3-benzo-thia-zole (C13H10N4O4S2), (II) and 2-[2-(3-nitro-benzene-sulfon-yl)hydrazin-yl]-1,3-benzo-thia-zol-3-ium 3-nitro-benzene-sulfonate (C13H11N4O4S2+·C6H4NO5S-), (III) are reported. Salt (I) arose from an unexpected reaction of 2-hydrazinylbenzo-thia-zole with the acetone solvent in the presence of 3-nitro-benzene-sulfonyl chloride, whereas (II) and (III) were recovered from the equivalent reaction carried out in methanol. The crystal of (I) features ion pairs linked by pairs of N-H⋯Os (s = sulfonate) hydrogen bonds; adjacent cations inter-act by way of short π-π stacking inter-actions between the thia-zole rings [centroid-centroid separation = 3.4274 (18) Å]. In (II), which crystallizes with two neutral mol-ecules in the asymmetric unit, the mol-ecules are linked by N-H⋯N and N-H⋯On (n = nitro) hydrogen bonds to generate [[Formula: see text]1[Formula: see text]] chains, which are cross-linked by C-H⋯O and π-π stacking inter-actions. The crystal of (III) features centrosymmetric tetra-mers (two cations and two anions) linked by cooperative N-H⋯O hydrogen bonds; C-H⋯O and π-π inter-actions occur between tetra-mers.

Highlights

The syntheses and crystal structures of 2-[2-(propan-2-ylidene)hydrazinyl]-1,3benzothiazol-3-ium 3-nitrobenzenesulfonate (C10H12N2S+ÁC6H4NO5SÀ), (I), 2-[2-(3-nitrobenzenesulfonyl)hydrazinyl]-1,3-benzothiazole (C13H10N4O4S2), (II) and 2-[2-(3-nitrobenzenesulfonyl)hydrazinyl]-1,3-benzothiazol-3-ium 3-nitrobenzenesulfonate (C13H11N4O4S2+ÁC6H4NO5SÀ), (III) are reported
The crystal of (I) features ion pairs linked by pairs of N—HÁ Á ÁOs (s = sulfonate) hydrogen bonds; adjacent cations interact by way of short – stacking interactions between the thiazole rings [centroid–centroid separation = 3.4274 (18) A ]
In (II), which crystallizes with two neutral molecules in the asymmetric unit, the molecules are linked by N—HÁ Á ÁN and N—HÁ Á ÁOn (n = nitro) hydrogen bonds to generate [111] chains, which are cross-linked by C— HÁ Á ÁO and – stacking interactions

Summary

Chemical context

Heteroaromatic benzothiazole derivatives are well-studied compounds, due in the main to their various and useful biological activities (for a review, see Gulati et al, 2017), and to their fluorescent and optical properties (e.g. Liu et al, 2018). Heteroaromatic benzothiazole derivatives are well-studied compounds, due in the main to their various and useful biological activities (for a review, see Gulati et al, 2017), and to their fluorescent and optical properties Hydrazonyl derivatives, 2-Ar—CH N—NH-benzothiazoles, formed from 2-hydrazinylbenzothiazole and ArCHO have attracted attention: for example, Katava et al (2017) have reported antitumor activities and Behera & Manivannan (2017) studied their use as sensors. Less attention has been paid generally to 2-(ArSO2NHNH)-benzothiazoles, antimicrobial activities have been briefly reported (Rao et al, 2005; Hipparagi et al, 2007). We have initiated a study of the syntheses, structures and biological activities of 2-(ArSO2NHNH)-benzothiazoles and we describe the structures of three products of the reactions of 2-hydrazinylbenzothiazole with 3-nitrobenzenesulfonyl chloride in different solvents, viz. We have initiated a study of the syntheses, structures and biological activities of 2-(ArSO2NHNH)-benzothiazoles and we describe the structures of three products of the reactions of 2-hydrazinylbenzothiazole with 3-nitrobenzenesulfonyl chloride in different solvents, viz. 2-[2-(propan-2-ylidene)hydrazinyl]-1,3-benzothiazol-3-ium 3-nitrobenzenesulfonate (I), 2-[2-(3-nitrobenzenesulfonyl)hydrazinyl]-1,3benzothiazole (II) and 2-[2-(3-nitrobenzenesulfonyl)hydrazinyl]-1,3-benzothiazol-3-ium 3-nitrobenzenesulfonate (III)

Structural commentary

Synthesis and crystallization

Refinement