The crystal structures and Hirshfeld surface analysis of three new bromo-substituted 3-methyl-1-(phenyl­sulfon­yl)-1H-indole derivatives

Abstract

The crystal structures of three new indole derivative are described. The supra­molecular relations in the system were assessed with a Hirshfeld surface analysis and calculation of the inter­action energies, which suggest a primary significance of π–π and C—H⋯π inter­actions involving the indole moieties.

Three new 1H-indole derivatives, namely, 2-(bromo­meth­yl)-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C₁₆H₁₄BrNO₂S, (I), 2-[(E)-2-(2-bromo-5-meth­oxy­phen­yl)ethen­yl]-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C₂₄H₂₀BrNO₃S, (II), and 2-[(E)-2-(2-bromo­phen­yl)ethen­yl]-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C₂₃H₁₈BrNO₂S, (III), exhibit nearly orthogonal orientations of their indole ring systems and sulfonyl-bound phenyl rings. Such conformations are favourable for inter­molecular bonding involving sets of slipped π–π inter­actions between the indole systems and mutual C—H⋯π hydrogen bonds, with the generation of two-dimensional monoperiodic patterns. The latter are found in all three structures, in the form of supra­molecular columns with every pair of successive mol­ecules related by inversion. The crystal packing of the compounds is additionally stabilized by weaker slipped π–π inter­actions between the outer phenyl rings (in II and III) and by weak C—H⋯O, C—H⋯Br and C—H⋯π hydrogen bonds. The structural significance of the different kinds of inter­actions agree with the results of a Hirshfeld surface analysis and the calculated inter­action energies. In particular, the largest inter­action energies (up to −60.8 kJ mol⁻¹) are associated with pairing of anti­parallel indole systems, while the energetics of weak hydrogen bonds and phenyl π–π inter­actions are comparable and account for 13–34 kJ mol⁻¹.