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

Madhan, S.; NizamMohideen, M.; Harikrishnan, K.; MohanaKrishnan, A.K.

doi:10.1107/S2056989024004985

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ISSN: 2056-9890

Volume 80| Part 6| June 2024| Pages 682-690

https://doi.org/10.1107/S2056989024004985

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

S. Madhan,^a M. NizamMohideen,^a ^* K. Harikrishnan ^b and Arasambattu K. MohanaKrishnan ^b

^aDepartment of Physics, The New College, Chennai 600 014, University of Madras, Tamil Nadu, India, and ^bDepartment of organic Chemistry, University of Madras, Guindy Campus, Chennai-600 025, Tamilnadu, India
^*Correspondence e-mail: mnizam.new@gmail.com

Edited by K. V. Domasevitch, National Taras Shevchenko University of Kyiv, Ukraine (Received 29 April 2024; accepted 27 May 2024; online 31 May 2024)

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.

Keywords: crystal structure; 1H-indole; phenylsulfonamide; π–π interactions; hydrogen bonding; Hirshfeld surface analysis.

CCDC references: 2358512; 2358511; 2358510

1. Chemical context

Derivatives of indole exhibit antibacterial (Okabe & Adachi, 1998 ) and antitumour (Schollmeyer et al., 1995 ) activities. In particular, 1-(phenylsulfonyl)indoles are applicable to the synthesis of biologically active alkaloids and their analogues, including pyridocarbazoles, such as the anticancer alkaloid ellipticine, carbazoles, furoindoles, pyrroloindoles, indolocarbazoles and other species. Some of the phenylsulfonyl indole compounds have been shown to inhibit the HIV-1 RT enzyme in vitro and HTLVIIIb viral spread in MT-4 human T-lymphoid cells (Williams et al., 1993 ). In such systems, the phenylsulfonyl moiety may act either as a protecting or an activating group (Jasinski et al., 2009 ). Since the related halogen-substituted indoles also demonstrate antibacterial and antifungal activity (Piscopo et al., 1990 ), one can anticipate a range of functional benefits from the halogen derivatization. Thus, substitution by bromine atoms may significantly enhance in vitro blood–brain barrier permeability, providing evidence for improved delivery to the central nervous system (Bouthenet et al., 2011 ). Bromination on the phenol ring is important for the antimicrobial activity (Gentry et al., 1999 ). The incorporation of heavy atoms, such as bromine, increases the generation of reactive species during photosensitization (Semenova et al., 2021 ). In particular, fluorescent Br-substituted dyes are utilized for photodynamic therapy applications (Liu et al., 2021 ). The fluorescent 4,6-dibromoindolenine cyanine revealed excellent properties for optical tumour imaging (Guerrero et al., 2017 ). Recognizing the importance of such compounds for biochemical applications and drug discovery and our ongoing research into the construction of indole derivatives have prompted us to investigate a series of Br-substituted species. We report herein the crystal structures determination and Hirshfeld surface analysis of three new indoles: 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 (III).

2. Structural commentary

The molecular structures of the title compounds, C₁₆H₁₄BrNO₂S, (I), C₂₄H₂₀BrNO₃S, (II) and C₂₃H₁₈BrNO₂S, (III), are illustrated in Figs. 1, 2 and 3, respectively. In all the cases, the indole ring systems (N1/C1–C8) are essentially planar, with a maximum deviation from the corresponding mean plane of 0.0393 (17) Å, observed for N1 atom in III. The sulfonyl-bound phenyl rings (C9–C14) are almost orthogonal to the carrier indole ring systems (N1/C1–C8), with respective interplanar angles of 76.40 (9)° for I, 73.35 (7)° for II and 87.68 (8)° for III. The ethenyl-bound phenyl rings (C17–C22) in II and III are also actually orthogonal to the indole frameworks, subtending dihedral angles of 72.48 (7) and 79.50 (8)°, respectively. As a consequence, the planes of these outer phenyl rings (C9–C14 and C17–C22) are nearly parallel, subtending angles of 9.56 (16) in II and 18.45 (6)° in III.

Figure 1
The molecular structure of compound I, with atom labelling and displacement ellipsoids drawn at the 30% probability level. The dashed line indicates the intramolecular hydrogen bond.

Figure 2
The molecular structure of compound II, with atom labelling and displacement ellipsoids drawn at the 30% probability level. The dashed line indicates the intramolecular hydrogen bond.

Figure 3
The molecular structure of compound III, with atom labelling and displacement ellipsoids drawn at the 30% probability level. The dashed line indicates the intramolecular hydrogen bond.

The torsion angles O2—S1—N1—C1 and O1—S1—N1—C8 [55.3 (2) and −21.1 (2)°, respectively, for I, −46.74 (19) and 45.94 (19)° for II and 42.9 (2) and −41.8 (2)° for III] indicate the syn conformation of the sulfonyl moiety. In all three compounds, the tetrahedral configuration around S1 atom is somewhat distorted. The increase in the O2—S1—O1 angles [120.11 (14)° for I, 119.67 (12)° for II and 119.60 (13)° for III], with a simultaneous decrease in the N1—S1—C9 angles [104.46 (12)° for I, 103.78 (10)° for II and 105.70 (10)° for III] from the ideal tetrahedral value (109.5°) are attributed to the Thorpe–Ingold effect (Bassindale, 1984 ). The widening of the angles may be due to the repulsive interaction between the two short S=O bonds.

In all three compounds, the sum of the bond angles around N1 [355.88 (11), 348.62 (17) and 352.89 (12)° for I, II and III, respectively] indicate sp² hybridization (Beddoes et al., 1986 ). At the same time, as a result of the electron-withdrawing character of the phenylsulfonyl groups, the N1—Csp² bonds are longer than the standard length value of 1.355 (14) Å [N1—C1 = 1.419 (3) for I, 1.425 (3) for II and 1.428 (3) Å for III and N1—C8 = 1.434 (3) for I, 1.438 (3) for II and 1.437 (3) Å for III] (Allen et al., 1987 ; Cambridge Structural Database (CSD), Version 5.37; Groom et al., 2016 ). In all the compounds, the certain expansion of the ipso angles at atoms C1, C3 and C4, and the contraction of the apical angles at atoms C2, C5 and C6 are caused by fusion of the smaller pyrrole ring with the six-membered benzene ring and the strain is taken up by the angular distortion rather than by bond-length distortion (Allen, 1981 ). The geometric parameters of the present compounds agree well with those reported for related structures (Madhan et al., 2022 , 2023a ,b ). In all three compounds, the molecular conformations are stabilized by weak C2—H2⋯O2 intramolecular interactions with C2⋯O2 = 2.950 (2)–3.057 (4) Å.

3. Supramolecular features

With a lack of conventional hydrogen-bond donor functionality, the supramolecular structures of all three compounds are dominated by weaker interactions, namely by weak C—H⋯O, C—H⋯Br and C—H⋯π hydrogen bonds (Tables 1–3 ) and slipped π–π stacking interactions (Table 4).

Table 1
Hydrogen-bond geometry (Å, °) for I

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2	0.93	2.49	3.057 (4)	120
C2—H2⋯O1ⁱ	0.93	2.71	3.503 (4)	144
C10—H10⋯O1ⁱ	0.93	2.53	3.306 (4)	141
C12—H12⋯O2ⁱⁱ	0.93	2.77	3.302 (5)	118
C13—H13⋯O2ⁱⁱ	0.93	2.92	3.376 (4)	112
C16—H16C⋯O2ⁱⁱⁱ	0.96	2.76	3.702 (4)	168
C4—H4⋯Br1^iv	0.93	3.16	3.905 (4)	138
C12—H12⋯Br1^v	0.93	3.16	3.922 (4)	141
C14—H14⋯Br1	0.93	2.99	3.894 (4)	165
C16—H16A⋯Cg(C9–C14)^vi	0.96	2.97	3.765 (4)	142
C16—H16B⋯Cg(C1–C6)^vii	0.96	2.97	3.823 (5)	149
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) ; (iii) ; (iv) ; (v) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (vi) $[x, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ ; (vii) .

Table 2
Hydrogen-bond geometry (Å, °) for II

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2	0.93	2.39	2.958 (4)	119
C3—H3⋯O2ⁱ	0.93	2.61	3.448 (3)	150
C24—H24A⋯Br1ⁱⁱ	0.96	3.03	3.699 (3)	128
C5—H5⋯Cg(C9–C14)ⁱⁱⁱ	0.93	3.12	4.047 (3)	173
C20—H20⋯Cg(C17–C22)^iv	0.93	3.15	3.978 (2)	149
C23—H23C⋯Cg(C1–C6)ⁱⁱⁱ	0.96	3.11	4.036 (4)	162
Symmetry codes: (i) ; (ii) $[x-1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) ; (iv) $[x, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ .

Table 3
Hydrogen-bond geometry (Å, °) for III

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O2	0.93	2.37	2.949 (5)	120
C13—H13⋯O1ⁱ	0.93	2.73	3.420 (3)	132
C14—H14⋯O2ⁱⁱ	0.93	2.77	3.547 (4)	142
C19—H19⋯Br1ⁱⁱⁱ	0.93	2.94	3.805 (3)	155
C5—H5⋯Cg(C9–C14)^iv	0.93	2.96	3.806 (4)	153
C23—H23A⋯Cg(C1–C6)^iv	0.96	3.21	3.999 (3)	110
C23—H23B⋯Cg(N1/C1/C6–C8)^v	0.96	3.12	3.561 (3)	149
Symmetry codes: (i) ; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iii) ; (iv) ; (v) .

Table 4
Geometry of stacking interactions (Å, °) for I–III

Cg is a group centroid; plane⋯CgB is the distance between the mean plane of Group A and the centroid of the interacting Group B; ipa is the interplanar angle; sa is the slippage angle, which is the angle of the CgA⋯CgB axis to the Group A mean plane normal.

Compound	Group A	Group B	Shortest contacts	CgA⋯CgB	Plane⋯CgB	ipa	sa
I	(N1/C1–C8)	(N1/C1–C8)ⁱⁱⁱ	3.573 (4)	3.628 (2)	3.551 (2)	0	11.8 (2)
	(N1/C1–C8)	(C1–C6)ⁱⁱⁱ	3.573 (4)	3.831 (2)	3.552 (2)	0.16 (14)	22.0 (2)
II	(N1/C1–C8)	(N1/C1–C8)^v	3.618 (3)	3.692 (2)	3.633 (2)	0	10.3 (2)
	(N1/C1–C8)	(C1–C6)^v	3.618 (3)	3.975 (2)	3.635 (2)	0.62 (13)	23.9 (2)
	(C17–C22)	(C19–C14)^vii	3.463 (3)	3.836 (3)	3.646 (3)	9.56 (16)	18.1 (2)
III	(C17–C22)	(C9–C14)^vi	3.381 (3)	3.742 (2)	3.379 (2)	10.34 (7)	24.5 (2)
	(C17–C22)	(C17–C22)^vii	3.489 (3)	3.691 (2)	3.488 (2)	0	19.1 (2)
Symmetry codes for I: (iii) −x + 1, −y + 1, −z + 1; for II: (v) −x + 1, −y + 1, −z + 1; (vii) x, y, z − 1; for III: (vi) −x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vii) −x + 2, −y + 2, −z + 1.

In the structure of I, molecules are linked via double bonds involving C2—H2 and C10—H10 donors and O1ⁱ acceptors [C⋯O = 3.306 (4) and 3.503 (4) Å; symmetry code: (i) −x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ] into the chains propagating along the b-axis direction in the crystal (Table 1). The most salient feature of the array is infinite stacking of the indole moieties, which yields columns down the a-axis. Within these columns, pairs of adjacent molecules are held together by π–π interactions or by double CH₃⋯π bonds, in alternate sequence (Fig. 4). The counterparts of every such pairs are related by inversion [symmetry codes: (iii) −x + 1, −y + 1, −x + 1; (v) −x, −y + 1, −z + 1, respectively.] For the dimer of the first kind, the geometry parameters are consistent with weak slipped π–π interactions. The shortest intercentroid distance is observed between the pyrrole rings (Table 4). However, the centroid of the N1/C1–C8 group (Cg1) is situated almost above the midpoint of the C1 and C6 bridgehead atoms of the neighbouring molecule and therefore both pyrrole–pyrrole [Cg1⋯Cg1ⁱⁱⁱ = 3.628 (3) Å] and pyrrole–benzo [Cg1⋯Cg2ⁱⁱⁱ = 3.831 (3) Å] interactions may be considered. The entire π–π and CH₃⋯π bonded stack is additionally stabilized by weak hydrogen bonding of the sulfonyl O atoms [C⋯O = 3.302 (5)–3.702 (4) Å]. One can note the functional importance of the methyl group, which is a donor of three highly directional interactions, viz. the C—H⋯O bond and two C—H⋯π bonds (Table 1).

Figure 4
(a) Fragment of the structure of I showing a column of molecules, down the a-axis in the crystal, sustained by π–π interactions and weak CH⋯π and CH⋯O bonds. (b) Projection of the structure nearly down the a-axis showing weak CH⋯O bonds between the columns (which are orthogonal to the drawing plane). Light-blue lines indicate the π–π interactions. [Symmetry codes: (i) x + 1, y − $[{1\over 2}]$ , −z + 1.5; (iii) x + 1, −y + 1, −z + 1; (vi) x, −y + 1.5, z − $[{1\over 2}]$ ; (vii) −x, −y + 1, −z + 1; (viii) x + 1, y, z.]

The structure of II inherits the above motif (Fig. 5). In particular, a combination of π–π and CH₃⋯π interactions assembles the molecules into columns propagating along the a-axis direction in the crystal, in exactly the same manner as observed for compound I. In this case, the interactions are slightly weaker and the corresponding intercentroid distances [Cg1⋯Cg1^v = 3.692 (3) Å; symmetry code: (v) −x + 1, −y + 1, −z + 1] are slightly larger compared with II (Table 4). The outer 2-bromo-5-methoxyphenyl rings also contribute to the packing pattern since they afford π–π interactions with the sulfonyl-bound C9–C14 rings, with typical intercentroid separations of 3.836 (2) Å and a relatively small slippage angle of 18.1 (2)° (Table 4). This stacking complements the weak C3—H3⋯O2ⁱ hydrogen bonds [C⋯O = 3.448 (3) Å; symmetry code: (i) −x + 1, −y + 1, −z], linking the columns of molecules in the c-axis direction (Fig. 5). There are no hydrogen-bonding interactions with the methoxy O3 atoms, which instead are involved in relatively short Br⋯O contacts of 3.3066 (19) Å. Very distal contacts of the type C24⋯Cg4^ix [4.098 (3) Å; Cg4 is the ring C17–C22 centroid; symmetry code: (ix) x, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ] possibly indicate weak C—H⋯π interactions.

Figure 5
(a) Fragment of the structure of II, with columns of the molecules down the a-axis, held by π–π (represented by light blue lines) and CH⋯π bonds. Short Br1⋯O3^vi contacts [3.3066 (19) Å] are also shown. (b) π–π and CH⋯O interactions between the columns. [Symmetry codes: (i) x + 1, −y + 1, −z; (iii) x + 2, −y + 1, −z + 1; (v) x + 1, −y + 1, −z + 1; (vi) x + 1, y, z; (vii) x, y, z − 1.]

In the structure of III, the π–π interactions of the indole ring systems are eliminated since the shortest intercentroid distance exceeds 4.4 Å. However, the structure retains the double CH₃⋯π bonding between inversion-related molecules with C23⋯Cg1^v = 3.560 (3) Å [Cg1 is the centroid of the pyrrole ring N1/C1/C6–8; symmetry code: (v) −x + 1, −y + 2, −z + 1]. Moreover, these methyl groups also establish distal mutual contacts with the C1–C6 rings [C23⋯Cg2^iv = 3.999 (3) Å; symmetry code: (iv) −x + 1, −y + 1, −z + 1], which likely represent very weak CH₃⋯π bonding. These interactions act in synergy with a set of weak C13—H13⋯O1ⁱ and C19—H19⋯Br1ⁱⁱⁱ bonds (Table 3) to link the molecules into the columns down the b-axis direction (Fig. 6). Therefore, the main features of the patterns seen for I and II are preserved for III with only minor variations. At the same time, beyond the supramolecular columns, which are nearly intact for all three compounds, the bonding features for III are essentially different. Both kinds of the phenyl rings afford a set of π–π interactions with the generation of discrete tetramers (Fig. 6), with the central duo representing a stack of two antiparallel inversion-related bromophenyl groups [Cg4⋯Cg4^vii = 3.691 (2) Å; symmetry code: (vii) −x + 2, −y + 2, −z + 1.] This central fragment is extended by incorporation of two outer sulfonyl-bound phenyl groups [Cg4⋯Cg3^vi = 3.742 (2) Å; symmetry code: (vi) −x + $[{3\over 2}]$ , y + 0.5, −z + $[{1\over 2}]$ ].

Figure 6
(a) Fragment of the structure of III, showing mutual CH⋯π bonding of the inversion-related indole fragments and how CH⋯O and CH⋯Br bonds contribute to the stabilization of the supramolecular column. (b) Projection of the structure on the ac-plane. Note the extensive π–π interactions of the phenyl rings yielding four-decker sandwiches. The indole columns are orthogonal to the drawing plane. [Symmetry codes: (i) x, y − 1, z; (v) x + 1, −y + 2, −z + 1; (vi) x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vii) x + 2, −y + 2, −z + 1.]

4. Hirshfeld surface analysis

The supramolecular interactions in the title structure were further assessed by Hirshfeld surface analysis. The Hirshfeld surfaces and 2D fingerprint plots were generated using CrystalExplorer21 software (Spackman et al., 2021 ).

The two-dimensional fingerprint plots (Parkin et al., 2007 ) detailing the various interactions for the molecules are shown in Fig. 7. For all three compounds, Hirshfeld surfaces suggest the dominance of contacts with the hydrogen atoms, accounting for over 90% of the contacts. Beyond the largest fractions of H⋯H contacts (38.7–44.7%), the principal contributors are C⋯H/H⋯C (20.4–25.7%), O⋯H/H⋯O (14.6–17.9%) and Br⋯H/H⋯Br (8.2–12.6%) contacts corresponding to the different kinds of C—H⋯π, C—H⋯O or C—H⋯Br bonds. Every type of such bonding is readily identified by the plots representing pairs of diffuse spikes pointing to the lower left. One can note a common trend for suppression of such hydrogen bonding in II and III. For example, the contribution of the O⋯H/H⋯O contacts for I (17.9%) is perceptibly larger than for II (14.6%), which incorporates an additional methoxy O atom. This effect may be attributed to the increasing significance of π–π interactions for the crystal packing in the case of II and III, in line with the increased number of aromatic groups. In addition, a slight reduction in the Br⋯H/H⋯Br contacts (12.6% for I versus 8.2% and 8.6% for II and III, respectively) may be reflective of a weaker acceptor ability of the phenyl-bound Br atoms with respect to the bromomethyl moieties in I. An overlap between nearly parallel aromatic frames, due to the slipped π–π stacking, is clearly indicated by the C⋯C plots for all compounds, in the form of the blue–green area centred at ca d_e = d_i = 1.85 Å. The plots suggest a progressive growth of the significance of these interactions, when moving from I to II and III. In line with this, the contributions of the C⋯C contacts to the entire surfaces are 2.5%, 6.3% and 8.2%, respectively. In the case of II, the peculiar short Br⋯O contacts are also readily identified by the fingerprint plots and they contribute as much as 1.6% to the surface area (Fig. 7).

Figure 7
Two-dimensional fingerprint plots for I–III and delineated into the principal contributions of H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, Br⋯H/H⋯Br, C⋯C, N⋯C/C⋯N, Br⋯O/O⋯Br and N⋯H/H⋯N contacts. Other contributors account for less than 1.0% contacts to the surface areas.

The interaction energy between the molecules is expressed in terms of four components: electrostatic, polarization, dispersion and exchange repulsion. These energies were obtained using monomer wavefunctions calculated at the B3LYP/6-31G(d,p) level. The total interaction energy, which is the sum of scaled components, was calculated for a 3.8 Å radius cluster of molecules around the selected molecule. The scale factors used in the CE-B3LYP bench research marked energy model (Mackenzie et al., 2017 ) are given in Table 5. The principal interaction pathways for I–III are shown in Figs. 8–10 , respectively. The interaction energies calculated by the energy model reveal that the interactions in the crystal have a significant contribution from dispersion components. It is worth noting that the primary forces for the crystal packing are associated with different stackings of the indole moieties. Either π–π or double CH⋯π interactions of the inversion-related molecules are equally important and they are particularly prevalent in the case of I. Thus, the highest energy E_tot = −60.8 kJ mol⁻¹ corresponds to the pairing pattern of type A (Fig. 8), with contributions from slipped π–π interactions and double C—H⋯O hydrogen bonding. In addition, short contacts of the methylene groups C15 and C3—C4 bonds [C15⋯Cg(C3/C4)ⁱⁱⁱ = 3.412 (2) Å; symmetry code: (iii) −x + 1, −y + 1, −z + 1] possibly reflect a kind of weak tetrel C⋯π bonding. The energies of other types of indole/indole interactions for II and III are comparable [E_tot = −43.1 to −55.1 kJ mol⁻¹] and the primary contributor here is London dispersion [up to −78.4 kJ mol⁻¹], in accordance with the very large interaction areas. The energies of the slipped π–π interactions of the phenyl rings in II and III are very similar and they account for −28.9 to −33.9 kJ mol⁻¹ (Table 4). The significance of these interactions is comparable with weak C—H⋯O hydrogen bonds. The energies of the latter themselves are only medium, for example −13.1 kJ mol⁻¹ (Type D) in I and −15.7 kJ mol⁻¹ (Type F) in II. However, pairing of the molecules via multiple hydrogen bonding increases the interaction energies up to −28.9 kJ mol⁻¹ (Type C in II, Fig. 9). This rich landscape of bonding modes, with a specific hierarchy of interaction energies, could be applicable as a model for supramolecular interactions of phenylsulfonyl-substituted indoles and their targeting of biomedical substrates.

Table 5
Calculated interaction energies (kJ mol⁻¹) for I–III

Interaction energies were calculated employing the CE-B3LYP/6–31G(d,p) functional/basis set combination. The scale factors used to determine E_tot were: k_ele = 1.057, k_pol = 0.740, k_dis = 0.871, and k_rep = 0.618 (Mackenzie et al., 2017). For details of the interaction modes, see Figs. 8–10 ; R is the distance in Å between the centroids of interacting molecules.

Type	Symmetry code	Interaction	R	E_ele	E_pol	E_dis	E_rep	E_tot
Compound I
A	−x + 1, −y + 1, −z + 1	π–π, CH⋯O	6.45	−20.2	−4.5	−71.5	42.4	−60.8
B	−x, −y + 1, −z + 1	CH–π	6.35	−10.5	−2.0	−59.9	32.8	−44.4
C	−x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$	CH⋯O	7.79	−7.9	−3.6	−22.8	14.0	−22.2
D	x − 1, y, z	CH⋯O	7.98	−5.7	−2.0	−10.6	6.0	−13.1
E	x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$	CH⋯Br, CH⋯π	9.09	−5.0	−0.9	−18.6	10.4	−15.7
F	−x, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$	CH⋯Br	9.03	−2.3	−1.0	−17.8	8.5	−13.4
Compound II
A	−x + 1, −y + 1, −z + 1	π–π	8.08	−8.9	−2.9	−67.3	29.0	−52.3
B	−x + 2, −y + 1, −z + 1	CH—π	8.10	−15.7	−1.7	−67.9	44.6	−49.4
C	−x + 1, −y + 1, −z	CH⋯O	12.70	−12.6	−2.9	−15.4	0.0	−28.9
D	x + 1, y, z	CH⋯O	8.43	−7.1	−2.2	−18.7	13.6	−17.1
E	x, y, z − 1	π–π	8.95	−4.2	−2.6	−47.8	22.8	−33.9
F	x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$	CH⋯Br, CH⋯π	8.77	−6.2	−2.2	−38.6	20.2	−29.3
Compound III
A	−x + 1, −y + 1, −z + 1	CH⋯π, dispersion	7.64	−11.5	−1.9	−78.4	43.3	−55.1
B	−x + 1, −y + 2, −z + 1	CH⋯π	7.91	−9.3	−2.0	−57.5	29.5	−43.1
C	−x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$	π–π	7.85	−7.1	−1.7	−40.7	21.3	−31.0
D	−x + 2, −y + 2, −z + 1	π–π	9.91	−5.2	−1.1	−50.4	34.5	−28.9
E	x, y − 1, z	CH⋯O, CH⋯Br	8.35	−10.5	−2.7	−28.3	21.7	−24.3
F	−x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$	CH⋯O	10.52	−3.6	−2.7	−15.6	6.0	−15.7

Figure 8
The principal pathways of the intermolecular interactions for I representing π–π and weak hydrogen bonding, with a cut-off limit for calculated energies of 6.0 kJ mol⁻¹. [Symmetry codes: (i) x + 1, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (ii) x − 1, −y + $[{1\over 2}]$ , z + $[{1\over 2}]$ ; (iii) x + 1, −y + 1, −z + 1; (v) x, y − $[{1\over 2}]$ , −z + $[{3\over 2}]$ ; (vi) x, −y + $[{3\over 2}]$ , z − $[{1\over 2}]$ .]

Figure 9
The principal pathways of the intermolecular interactions for II representing π–π and weak hydrogen bonding, with a cut-off limit for calculated energies of 12.0 kJ mol⁻¹. [Symmetry codes: (i) x + 1, −y + 1, −z; (iii) x + 2, −y + 1, −z + 1; (v) x + 1, −y + 1, −z + 1; (vi) x + 1, y, z; (vii) x, y, z − 1; (viii) x, −y + $[{1\over 2}]$ , z − $[{1\over 2}]$ .]

Figure 10
The principal pathways of the intermolecular interactions for II representing π–π and weak hydrogen bonding, with a cut-off limit for calculated energies of 6.0 kJ mol⁻¹. [Symmetry codes: (i) x, y − 1, z; (ii) x + $[{1\over 2}]$ , y − $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (iv) x + 1, −y + 1, −z + 1; (v) x + 1, −y + 2, −z + 1; (vi) x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , −z + $[{1\over 2}]$ ; (vii) x + 2, −y + 2, −z + 1.]

5. Database survey

A search of the Cambridge Structural Database (Version 5.37; Groom et al., 2016). indicated 123 compounds incorporating a phenylsulfonyl-1H-indole moiety. Of these compounds, several similar structures have been reported earlier, i.e. ethyl 2-acetoxymethyl-1-phenylsulfonyl-1H-indole-3-carboxylate (Gunasekaran et al., 2009 ), 3-iodo-2-methyl-1-phenylsulfonyl-1H-indole (Ramathilagam et al., 2011 ) and 1-(2-bromomethyl-1-phenylsulfonyl-1H-indol-3-yl)propan-1-one (Umadevi et al., 2013 ). In these structures, the sulfonyl-bound phenyl rings are almost orthogonal to the indole ring systems, with corresponding dihedral angles of 83.35 (5), 82.84 (9) and 89.91 (11)°, respectively, being comparable with those in the present three compounds.

6. Synthesis and crystallization

Compound I: To a mixture of N-phenylsulfonyl-3-methylindole (6.00 g, 22.22 mmol) and paraformaldehyde (3.33 g, 111.1 mmol) in 50 ml of dry CCl₄, a 33 wt % solution HBr in acetic acid (13.46 ml) was added rapidly. The mixture was kept at room temperature for 6 h. After completion of the reaction (monitored by TLC), the mixture was poured into 100 ml of ice–water and then extracted with CCl₄ (2 × 20 ml). The extract was dried with Na₂SO₄. Removal of the solvent in vacuo followed by crystallization from methanol (4 ml) afforded compound I as a colourless solid (yield: 6.9 g, 86%).

Compound II: To a suspension of hexane (5 mL) washed NaH (0.43 g, 10.92 mmol) in dry THF (5 ml), a solution of diethyl {[3-methyl-1-(phenylsulfonyl)-1H-indol-2-yl]methyl}phosphonate (2.30 g, 5.46 mmol) in dry THF (10 ml) was slowly added via an addition funnel at 283 K under an N₂ atmosphere and stirred for 15 min. Then a solution of 2-bromo-5-methoxybenzaldehyde (1.39 g, 6.55 mmol) in dry THF (5 ml) was added and the mixture was allowed to stir for an additional 1 h. After completion of the reaction (monitored by TLC), the mixture was poured over crushed ice (100 g) containing concentrated HCl (1 ml). The solid formed was filtered and washed with methanol. Recrystallization from methanol (4 ml) afforded compound II as a bright-yellow solid (yield: 2.00 g, 76%). M.p. = 425–427 K.

Compound III: To a suspension of hexane (5 mL) washed NaH (0.38 g, 9.50 mmol) in dry THF (5 ml), a solution of diethyl {[3-methyl-1-(phenylsulfonyl)-1H-indol-2-yl]methyl}phosphonate (2.00 g, 4.75 mmol) in dry THF (10 ml) was slowly added via an addition funnel at 283 K under an N₂ atmosphere and stirred for 15 min. Then a solution of 2-bromobenzaldehyde (1.05 g, 5.70 mmol) in dry THF (5 ml) was added and the mixture was allowed to stir for an additional 1 h. After completion of the reaction (monitored by TLC), the mixture was poured over crushed ice (100 g) containing concentrated HCl (1 ml). The solid formed was filtered and washed with methanol to afford ethenylindole III as a bright-yellow solid (yield: 1.72 g, 71%). M.p. = 419-421 K.

7. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 6. All C-bound H atoms were positioned geometrically and constrained to ride on their parent atoms with C—H = 0.93–0.97 Å with U_iso(H) = 1.5U_eq(C-methyl) and 1.2U_eq(C) for other H atoms.

Table 6
Experimental details

	I	II	III
Crystal data
Chemical formula	C₁₆H₁₄BrNO₂S	C₂₄H₂₀BrNO₃S	C₂₃H₁₈BrNO₂S
M_r	364.25	482.38	452.35
Crystal system, space group	Monoclinic, P2₁/c	Monoclinic, P2₁/c	Monoclinic, P2₁/n
Temperature (K)	298	298	298
a, b, c (Å)	7.979 (6), 11.100 (8), 17.540 (14)	8.4252 (9), 28.669 (3), 8.9462 (11)	12.5530 (8), 8.3533 (5), 19.7698 (11)
β (°)	99.04 (3)	95.445 (4)	107.078 (2)
V (Å³)	1534 (2)	2151.1 (4)	1981.6 (2)
Z	4	4	4
Radiation type	Mo Kα	Mo Kα	Mo Kα
μ (mm⁻¹)	2.82	2.03	2.20
Crystal size (mm)	0.30 × 0.24 × 0.07	0.25 × 0.20 × 0.13	0.36 × 0.31 × 0.24

Data collection
Diffractometer	Bruker D8 Venture Diffractometer	Bruker D8 Venture Diffractometer	Bruker D8 Venture Diffractometer
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )	Multi-scan (SADABS; Krause et al., 2015)	Multi-scan (SADABS; Krause et al., 2015)
T_min, T_max	0.589, 0.753	0.555, 0.745	0.514, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	66991, 4464, 3158	52479, 5296, 3905	50531, 4293, 3516
R_int	0.049	0.077	0.058
(sin θ/λ)_max (Å⁻¹)	0.704	0.666	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.118, 1.10	0.039, 0.099, 1.03	0.036, 0.087, 1.10
No. of reflections	4464	5296	4293
No. of parameters	191	272	254
H-atom treatment	H-atom parameters constrained	H-atom parameters constrained	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.75, −0.80	0.39, −0.68	0.37, −0.32
Computer programs: APEX2 and SAINT (Bruker, 2016 ), SHELXS2018/3 (Sheldrick, 2008 ), SHELXL2018/3 (Sheldrick, 2015 ), ORTEP-3 for Windows and WinGX (Farrugia, 2012 ), Mercury (Macrae et al., 2020 ), publCIF (Westrip, 2010 ) and PLATON (Spek, 2020 ).

Supporting information

CCDC references: 2358512; 2358511; 2358510

Crystal structure: contains datablocks global, I, II, III. DOI: https://doi.org/10.1107/S2056989024004985/nu2005sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989024004985/nu2005Isup2.hkl

Structure factors: contains datablock II. DOI: https://doi.org/10.1107/S2056989024004985/nu2005IIsup3.hkl

Structure factors: contains datablock III. DOI: https://doi.org/10.1107/S2056989024004985/nu2005IIIsup4.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989024004985/nu2005Isup5.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989024004985/nu2005IIsup6.cml

Supporting information file. DOI: https://doi.org/10.1107/S2056989024004985/nu2005IIIsup7.cml

checkCIF report

Computing details top

2-(Bromomethyl)-3-methyl-1-(phenylsulfonyl)-1H-indole (I) top

Crystal data top

C₁₆H₁₄BrNO₂S	F(000) = 736
M_r = 364.25	D_x = 1.577 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.979 (6) Å	Cell parameters from 66991 reflections
b = 11.100 (8) Å	θ = 1.4–25.0°
c = 17.540 (14) Å	µ = 2.82 mm⁻¹
β = 99.04 (3)°	T = 298 K
V = 1534 (2) Å³	Prism, colorless
Z = 4	0.30 × 0.24 × 0.07 mm

Data collection top

Bruker D8 Venture Diffractometer	3158 reflections with I > 2σ(I)
Radiation source: micro focus sealed tube	R_int = 0.049
ω and φ scans	θ_max = 30.0°, θ_min = 3.2°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→10
T_min = 0.589, T_max = 0.753	k = −15→15
66991 measured reflections	l = −24→24
4464 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0434P)² + 1.2291P] where P = (F_o² + 2F_c²)/3
4464 reflections	(Δ/σ)_max = 0.001
191 parameters	Δρ_max = 0.75 e Å⁻³
0 restraints	Δρ_min = −0.80 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3530 (3)	0.4783 (2)	0.58255 (14)	0.0345 (5)
C2	0.3824 (3)	0.3757 (2)	0.62843 (16)	0.0439 (6)
H2	0.446932	0.378932	0.677377	0.053*
C3	0.3113 (4)	0.2684 (2)	0.59810 (18)	0.0513 (7)
H3	0.328360	0.198413	0.627406	0.062*
C4	0.2149 (4)	0.2635 (3)	0.5247 (2)	0.0570 (7)
H4	0.168902	0.190393	0.505784	0.068*
C5	0.1868 (4)	0.3654 (3)	0.47978 (18)	0.0526 (7)
H5	0.122660	0.361549	0.430761	0.063*
C6	0.2562 (3)	0.4750 (2)	0.50893 (14)	0.0387 (5)
C7	0.2515 (3)	0.5952 (2)	0.47726 (15)	0.0428 (6)
C8	0.3405 (3)	0.6691 (2)	0.53034 (14)	0.0398 (5)
C9	0.2921 (3)	0.6242 (2)	0.73345 (14)	0.0385 (5)
C10	0.2971 (4)	0.5343 (3)	0.78836 (17)	0.0537 (7)
H10	0.395387	0.489561	0.803309	0.064*
C11	0.1513 (5)	0.5123 (3)	0.8207 (2)	0.0656 (9)
H11	0.151977	0.452309	0.857811	0.079*
C12	0.0065 (4)	0.5786 (3)	0.7982 (2)	0.0620 (8)
H12	−0.090984	0.562026	0.819260	0.074*
C13	0.0053 (4)	0.6692 (3)	0.74490 (18)	0.0585 (8)
H13	−0.092489	0.714723	0.730838	0.070*
C14	0.1477 (3)	0.6933 (3)	0.71194 (15)	0.0482 (6)
H14	0.146765	0.754810	0.675899	0.058*
C15	0.3845 (4)	0.7966 (2)	0.51928 (19)	0.0540 (7)
H15A	0.397273	0.808599	0.465716	0.065*
H15B	0.493150	0.813659	0.550710	0.065*
C16	0.1665 (5)	0.6285 (3)	0.39759 (17)	0.0642 (9)
H16A	0.177941	0.713609	0.389959	0.096*
H16B	0.048275	0.607924	0.391753	0.096*
H16C	0.218751	0.585444	0.360103	0.096*
N1	0.4082 (3)	0.59886 (17)	0.59670 (12)	0.0369 (4)
O1	0.5039 (3)	0.77321 (19)	0.68162 (13)	0.0614 (6)
O2	0.6017 (2)	0.5675 (2)	0.72121 (13)	0.0596 (6)
S1	0.47047 (8)	0.64724 (6)	0.68698 (4)	0.04217 (16)
Br1	0.21361 (5)	0.91337 (3)	0.54636 (2)	0.07195 (15)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0357 (11)	0.0336 (11)	0.0354 (12)	−0.0001 (9)	0.0087 (9)	−0.0030 (9)
C2	0.0492 (14)	0.0417 (13)	0.0413 (13)	0.0019 (11)	0.0085 (11)	0.0015 (11)
C3	0.0574 (17)	0.0350 (13)	0.0632 (18)	0.0002 (12)	0.0148 (14)	0.0037 (12)
C4	0.0605 (18)	0.0385 (14)	0.071 (2)	−0.0082 (13)	0.0083 (15)	−0.0132 (14)
C5	0.0523 (16)	0.0507 (16)	0.0517 (16)	0.0003 (13)	−0.0014 (13)	−0.0157 (13)
C6	0.0379 (12)	0.0400 (13)	0.0385 (13)	0.0043 (10)	0.0069 (10)	−0.0064 (10)
C7	0.0480 (14)	0.0442 (14)	0.0369 (12)	0.0126 (11)	0.0086 (11)	−0.0006 (11)
C8	0.0486 (14)	0.0343 (12)	0.0395 (13)	0.0082 (10)	0.0162 (11)	0.0029 (10)
C9	0.0442 (13)	0.0389 (12)	0.0319 (11)	−0.0030 (10)	0.0042 (10)	−0.0091 (10)
C10	0.0686 (19)	0.0485 (16)	0.0460 (15)	0.0103 (14)	0.0153 (14)	0.0029 (13)
C11	0.092 (3)	0.0532 (18)	0.0582 (19)	−0.0030 (17)	0.0335 (18)	0.0052 (15)
C12	0.0607 (19)	0.074 (2)	0.0563 (18)	−0.0052 (16)	0.0254 (15)	−0.0081 (16)
C13	0.0460 (15)	0.077 (2)	0.0536 (17)	0.0048 (15)	0.0101 (13)	−0.0018 (16)
C14	0.0479 (14)	0.0577 (17)	0.0382 (13)	0.0023 (13)	0.0042 (11)	0.0022 (12)
C15	0.0698 (19)	0.0387 (14)	0.0599 (18)	0.0037 (13)	0.0303 (15)	0.0048 (12)
C16	0.079 (2)	0.070 (2)	0.0418 (15)	0.0249 (18)	0.0027 (14)	0.0042 (15)
N1	0.0430 (11)	0.0327 (10)	0.0356 (10)	−0.0025 (8)	0.0082 (8)	−0.0037 (8)
O1	0.0733 (14)	0.0497 (12)	0.0623 (13)	−0.0260 (11)	0.0137 (11)	−0.0174 (10)
O2	0.0384 (10)	0.0789 (15)	0.0577 (12)	0.0025 (10)	−0.0047 (9)	−0.0067 (11)
S1	0.0380 (3)	0.0465 (4)	0.0413 (3)	−0.0093 (3)	0.0036 (2)	−0.0100 (3)
Br1	0.1035 (3)	0.03893 (17)	0.0794 (3)	0.01814 (16)	0.0331 (2)	0.00174 (15)

Geometric parameters (Å, º) top

C1—C2	1.393 (4)	C10—C11	1.394 (5)
C1—C6	1.397 (4)	C10—H10	0.9300
C1—N1	1.419 (3)	C11—C12	1.374 (5)
C2—C3	1.388 (4)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.372 (5)
C3—C4	1.393 (5)	C12—H12	0.9300
C3—H3	0.9300	C13—C14	1.379 (4)
C4—C5	1.377 (5)	C13—H13	0.9300
C4—H4	0.9300	C14—H14	0.9300
C5—C6	1.399 (4)	C15—Br1	1.992 (3)
C5—H5	0.9300	C15—H15A	0.9700
C6—C7	1.444 (4)	C15—H15B	0.9700
C7—C8	1.355 (4)	C16—H16A	0.9600
C7—C16	1.501 (4)	C16—H16B	0.9600
C8—N1	1.434 (3)	C16—H16C	0.9600
C8—C15	1.478 (4)	N1—S1	1.672 (2)
C9—C10	1.384 (4)	O1—S1	1.429 (2)
C9—C14	1.386 (4)	O2—S1	1.430 (2)
C9—S1	1.766 (3)

C2—C1—C6	122.0 (2)	C10—C11—H11	119.8
C2—C1—N1	130.6 (2)	C13—C12—C11	120.2 (3)
C6—C1—N1	107.3 (2)	C13—C12—H12	119.9
C3—C2—C1	117.3 (3)	C11—C12—H12	119.9
C3—C2—H2	121.4	C12—C13—C14	120.6 (3)
C1—C2—H2	121.4	C12—C13—H13	119.7
C2—C3—C4	121.4 (3)	C14—C13—H13	119.7
C2—C3—H3	119.3	C13—C14—C9	118.9 (3)
C4—C3—H3	119.3	C13—C14—H14	120.6
C5—C4—C3	120.9 (3)	C9—C14—H14	120.6
C5—C4—H4	119.6	C8—C15—Br1	113.97 (19)
C3—C4—H4	119.6	C8—C15—H15A	108.8
C4—C5—C6	119.1 (3)	Br1—C15—H15A	108.8
C4—C5—H5	120.5	C8—C15—H15B	108.8
C6—C5—H5	120.5	Br1—C15—H15B	108.8
C1—C6—C5	119.4 (2)	H15A—C15—H15B	107.7
C1—C6—C7	108.0 (2)	C7—C16—H16A	109.5
C5—C6—C7	132.7 (2)	C7—C16—H16B	109.5
C8—C7—C6	108.4 (2)	H16A—C16—H16B	109.5
C8—C7—C16	127.0 (3)	C7—C16—H16C	109.5
C6—C7—C16	124.5 (3)	H16A—C16—H16C	109.5
C7—C8—N1	108.6 (2)	H16B—C16—H16C	109.5
C7—C8—C15	126.8 (3)	C1—N1—C8	107.7 (2)
N1—C8—C15	124.0 (3)	C1—N1—S1	120.44 (16)
C10—C9—C14	121.4 (3)	C8—N1—S1	127.74 (17)
C10—C9—S1	119.2 (2)	O1—S1—O2	120.11 (14)
C14—C9—S1	119.4 (2)	O1—S1—N1	106.42 (12)
C9—C10—C11	118.4 (3)	O2—S1—N1	106.72 (12)
C9—C10—H10	120.8	O1—S1—C9	110.12 (13)
C11—C10—H10	120.8	O2—S1—C9	107.87 (14)
C12—C11—C10	120.5 (3)	N1—S1—C9	104.46 (12)
C12—C11—H11	119.8

C6—C1—C2—C3	0.0 (4)	C10—C9—C14—C13	−1.6 (4)
N1—C1—C2—C3	−179.5 (2)	S1—C9—C14—C13	175.7 (2)
C1—C2—C3—C4	0.2 (4)	C7—C8—C15—Br1	90.8 (3)
C2—C3—C4—C5	−0.1 (5)	N1—C8—C15—Br1	−98.9 (3)
C3—C4—C5—C6	−0.2 (5)	C2—C1—N1—C8	−179.5 (2)
C2—C1—C6—C5	−0.3 (4)	C6—C1—N1—C8	0.8 (3)
N1—C1—C6—C5	179.3 (2)	C2—C1—N1—S1	−20.7 (4)
C2—C1—C6—C7	−179.7 (2)	C6—C1—N1—S1	159.66 (17)
N1—C1—C6—C7	−0.1 (3)	C7—C8—N1—C1	−1.3 (3)
C4—C5—C6—C1	0.4 (4)	C15—C8—N1—C1	−173.2 (2)
C4—C5—C6—C7	179.6 (3)	C7—C8—N1—S1	−158.14 (19)
C1—C6—C7—C8	−0.8 (3)	C15—C8—N1—S1	30.0 (3)
C5—C6—C7—C8	179.9 (3)	C1—N1—S1—O1	−175.28 (19)
C1—C6—C7—C16	177.2 (3)	C8—N1—S1—O1	−21.1 (2)
C5—C6—C7—C16	−2.1 (5)	C1—N1—S1—O2	55.3 (2)
C6—C7—C8—N1	1.3 (3)	C8—N1—S1—O2	−150.5 (2)
C16—C7—C8—N1	−176.6 (3)	C1—N1—S1—C9	−58.8 (2)
C6—C7—C8—C15	172.8 (2)	C8—N1—S1—C9	95.4 (2)
C16—C7—C8—C15	−5.0 (5)	C10—C9—S1—O1	−136.9 (2)
C14—C9—C10—C11	1.5 (4)	C14—C9—S1—O1	45.7 (2)
S1—C9—C10—C11	−175.9 (2)	C10—C9—S1—O2	−4.1 (3)
C9—C10—C11—C12	0.1 (5)	C14—C9—S1—O2	178.5 (2)
C10—C11—C12—C13	−1.5 (5)	C10—C9—S1—N1	109.2 (2)
C11—C12—C13—C14	1.4 (5)	C14—C9—S1—N1	−68.2 (2)
C12—C13—C14—C9	0.2 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.49	3.057 (4)	120
C2—H2···O1ⁱ	0.93	2.71	3.503 (4)	144
C10—H10···O1ⁱ	0.93	2.53	3.306 (4)	141
C12—H12···O2ⁱⁱ	0.93	2.77	3.302 (5)	118
C13—H13···O2ⁱⁱ	0.93	2.92	3.376 (4)	112
C16—H16C···O2ⁱⁱⁱ	0.96	2.76	3.702 (4)	168
C4—H4···Br1^iv	0.93	3.16	3.905 (4)	138
C12—H12···Br1^v	0.93	3.16	3.922 (4)	141
C14—H14···Br1	0.93	2.99	3.894 (4)	165
C16—H16A···Cg(C9–C14)^vi	0.96	2.97	3.765 (4)	142
C16—H16B···Cg(C1–C6)^vii	0.96	2.97	3.823 (5)	149

Symmetry codes: (i) −x+1, y−1/2, −z+3/2; (ii) x−1, y, z; (iii) −x+1, −y+1, −z+1; (iv) x, y−1, z; (v) −x, y−1/2, −z+3/2; (vi) x, −y+3/2, z−1/2; (vii) −x, −y+1, −z+1.

2-[(E)-2-(2-Bromo-5-methoxyphenyl)ethenyl]-3-methyl-1-(phenylsulfonyl)-1H-indole (II) top

Crystal data top

C₂₄H₂₀BrNO₃S	F(000) = 984
M_r = 482.38	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.4252 (9) Å	Cell parameters from 52480 reflections
b = 28.669 (3) Å	θ = 1.4–25.0°
c = 8.9462 (11) Å	µ = 2.03 mm⁻¹
β = 95.445 (4)°	T = 298 K
V = 2151.1 (4) Å³	Solid, yellow
Z = 4	0.25 × 0.20 × 0.13 mm

Data collection top

Bruker D8 Venture Diffractometer	3905 reflections with I > 2σ(I)
Radiation source: micro focus sealed tube	R_int = 0.077
ω and φ scans	θ_max = 28.3°, θ_min = 3.3°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −11→11
T_min = 0.555, T_max = 0.745	k = −38→38
52479 measured reflections	l = −11→11
5296 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.099	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0367P)² + 1.0393P] where P = (F_o² + 2F_c²)/3
5296 reflections	(Δ/σ)_max = 0.001
272 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.6561 (3)	0.48550 (8)	0.3470 (2)	0.0469 (5)
C2	0.6281 (3)	0.50829 (10)	0.2093 (3)	0.0614 (6)
H2	0.568729	0.494387	0.128332	0.074*
C3	0.6923 (4)	0.55236 (11)	0.1981 (3)	0.0717 (8)
H3	0.676266	0.568262	0.107279	0.086*
C4	0.7791 (4)	0.57337 (10)	0.3175 (4)	0.0742 (8)
H4	0.820363	0.603085	0.305664	0.089*
C5	0.8062 (3)	0.55132 (9)	0.4542 (3)	0.0643 (7)
H5	0.863821	0.565906	0.534811	0.077*
C6	0.7446 (3)	0.50632 (8)	0.4686 (2)	0.0473 (5)
C7	0.7513 (3)	0.47458 (8)	0.5935 (2)	0.0461 (5)
C8	0.6716 (2)	0.43516 (7)	0.5475 (2)	0.0421 (4)
C9	0.7837 (3)	0.38292 (8)	0.2424 (3)	0.0489 (5)
C10	0.8684 (3)	0.35109 (10)	0.3337 (3)	0.0673 (7)
H10	0.820424	0.335580	0.408902	0.081*
C11	1.0261 (4)	0.34260 (13)	0.3116 (4)	0.0860 (10)
H11	1.084868	0.321232	0.372357	0.103*
C12	1.0964 (4)	0.36561 (13)	0.2001 (5)	0.0861 (10)
H12	1.202336	0.359691	0.185423	0.103*
C13	1.0103 (4)	0.39724 (12)	0.1108 (4)	0.0805 (9)
H13	1.058787	0.412993	0.036429	0.097*
C14	0.8539 (4)	0.40589 (10)	0.1299 (3)	0.0643 (7)
H14	0.795426	0.426986	0.067855	0.077*
C15	0.6383 (3)	0.39387 (8)	0.6346 (2)	0.0444 (5)
H15	0.536056	0.381323	0.623013	0.053*
C16	0.7478 (3)	0.37332 (7)	0.7300 (2)	0.0438 (5)
H16	0.851979	0.384173	0.732095	0.053*
C17	0.7170 (2)	0.33490 (7)	0.8319 (2)	0.0400 (4)
C18	0.5683 (3)	0.32918 (7)	0.8844 (2)	0.0438 (5)
H18	0.486448	0.349562	0.851587	0.053*
C19	0.5381 (3)	0.29388 (8)	0.9845 (3)	0.0490 (5)
C20	0.6587 (3)	0.26380 (9)	1.0366 (3)	0.0599 (6)
H20	0.639903	0.240384	1.104648	0.072*
C21	0.8074 (3)	0.26891 (8)	0.9866 (3)	0.0580 (6)
H21	0.889518	0.248965	1.022176	0.070*
C22	0.8361 (3)	0.30307 (7)	0.8848 (3)	0.0455 (5)
C23	0.8223 (4)	0.48672 (10)	0.7485 (3)	0.0681 (7)
H23A	0.791508	0.463736	0.818252	0.102*
H23B	0.784469	0.516817	0.776049	0.102*
H23C	0.936409	0.487396	0.750554	0.102*
C24	0.3489 (4)	0.25800 (13)	1.1295 (4)	0.0971 (12)
H24A	0.238662	0.260695	1.147390	0.146*
H24B	0.368142	0.227541	1.090527	0.146*
H24C	0.414581	0.262561	1.222022	0.146*
N1	0.6044 (2)	0.44108 (6)	0.39484 (19)	0.0449 (4)
O1	0.5205 (2)	0.35818 (6)	0.3525 (2)	0.0635 (5)
O2	0.5020 (2)	0.41358 (7)	0.1409 (2)	0.0722 (5)
O3	0.3861 (2)	0.29237 (7)	1.0239 (2)	0.0704 (5)
S1	0.58589 (7)	0.39595 (2)	0.27518 (6)	0.05060 (15)
Br1	1.04254 (3)	0.30608 (2)	0.81730 (3)	0.06603 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0452 (11)	0.0509 (12)	0.0454 (12)	0.0121 (9)	0.0092 (9)	0.0073 (10)
C2	0.0653 (16)	0.0700 (16)	0.0493 (13)	0.0168 (13)	0.0076 (11)	0.0139 (12)
C3	0.0784 (19)	0.0731 (18)	0.0660 (17)	0.0233 (15)	0.0194 (15)	0.0311 (15)
C4	0.0778 (19)	0.0526 (15)	0.096 (2)	0.0088 (14)	0.0262 (17)	0.0275 (15)
C5	0.0702 (17)	0.0495 (14)	0.0740 (17)	−0.0018 (12)	0.0115 (14)	0.0052 (13)
C6	0.0507 (12)	0.0435 (11)	0.0487 (12)	0.0066 (9)	0.0099 (10)	0.0047 (10)
C7	0.0494 (12)	0.0470 (12)	0.0419 (11)	0.0026 (9)	0.0044 (9)	0.0013 (9)
C8	0.0423 (11)	0.0477 (11)	0.0367 (10)	0.0055 (9)	0.0060 (8)	0.0032 (9)
C9	0.0481 (12)	0.0526 (13)	0.0459 (12)	−0.0051 (10)	0.0036 (10)	−0.0127 (10)
C10	0.0614 (16)	0.0698 (17)	0.0714 (17)	0.0112 (13)	0.0100 (13)	−0.0006 (14)
C11	0.0666 (19)	0.090 (2)	0.100 (2)	0.0239 (17)	0.0004 (18)	−0.0126 (19)
C12	0.0518 (16)	0.096 (2)	0.112 (3)	−0.0075 (16)	0.0195 (18)	−0.048 (2)
C13	0.082 (2)	0.080 (2)	0.086 (2)	−0.0191 (17)	0.0400 (18)	−0.0266 (18)
C14	0.0738 (17)	0.0673 (16)	0.0539 (14)	−0.0036 (13)	0.0167 (13)	−0.0091 (12)
C15	0.0440 (11)	0.0474 (12)	0.0425 (11)	−0.0010 (9)	0.0072 (9)	0.0013 (9)
C16	0.0408 (11)	0.0435 (11)	0.0477 (12)	0.0008 (9)	0.0069 (9)	−0.0008 (9)
C17	0.0424 (10)	0.0366 (10)	0.0399 (10)	0.0003 (8)	−0.0020 (8)	−0.0027 (8)
C18	0.0431 (11)	0.0431 (11)	0.0441 (11)	0.0017 (9)	−0.0021 (9)	0.0038 (9)
C19	0.0469 (12)	0.0514 (12)	0.0471 (12)	−0.0059 (10)	−0.0028 (10)	0.0076 (10)
C20	0.0614 (15)	0.0531 (14)	0.0631 (15)	−0.0030 (11)	−0.0060 (12)	0.0201 (12)
C21	0.0559 (14)	0.0472 (13)	0.0683 (16)	0.0097 (11)	−0.0081 (12)	0.0115 (12)
C22	0.0422 (11)	0.0425 (11)	0.0505 (12)	0.0036 (9)	−0.0022 (9)	−0.0057 (9)
C23	0.093 (2)	0.0577 (15)	0.0510 (14)	−0.0049 (14)	−0.0060 (14)	−0.0038 (12)
C24	0.079 (2)	0.110 (3)	0.106 (3)	−0.0124 (19)	0.0235 (19)	0.053 (2)
N1	0.0454 (9)	0.0490 (10)	0.0399 (9)	0.0047 (8)	0.0018 (7)	0.0024 (8)
O1	0.0581 (10)	0.0660 (11)	0.0666 (11)	−0.0193 (8)	0.0066 (8)	−0.0049 (9)
O2	0.0665 (11)	0.0939 (14)	0.0512 (10)	0.0062 (10)	−0.0195 (8)	−0.0042 (9)
O3	0.0510 (10)	0.0845 (13)	0.0760 (12)	−0.0058 (9)	0.0077 (9)	0.0337 (10)
S1	0.0441 (3)	0.0620 (4)	0.0443 (3)	−0.0022 (3)	−0.0033 (2)	−0.0053 (3)
Br1	0.04735 (15)	0.06198 (17)	0.0897 (2)	0.01104 (11)	0.01150 (13)	−0.00450 (14)

Geometric parameters (Å, º) top

C1—C6	1.393 (3)	C14—H14	0.9300
C1—C2	1.395 (3)	C15—C16	1.333 (3)
C1—N1	1.425 (3)	C15—H15	0.9300
C2—C3	1.382 (4)	C16—C17	1.469 (3)
C2—H2	0.9300	C16—H16	0.9300
C3—C4	1.375 (4)	C17—C18	1.389 (3)
C3—H3	0.9300	C17—C22	1.405 (3)
C4—C5	1.376 (4)	C18—C19	1.391 (3)
C4—H4	0.9300	C18—H18	0.9300
C5—C6	1.401 (3)	C19—O3	1.360 (3)
C5—H5	0.9300	C19—C20	1.380 (3)
C6—C7	1.438 (3)	C20—C21	1.377 (4)
C7—C8	1.358 (3)	C20—H20	0.9300
C7—C23	1.498 (3)	C21—C22	1.374 (3)
C8—N1	1.438 (3)	C21—H21	0.9300
C8—C15	1.459 (3)	C22—Br1	1.896 (2)
C9—C10	1.378 (4)	C23—H23A	0.9600
C9—C14	1.382 (3)	C23—H23B	0.9600
C9—S1	1.759 (2)	C23—H23C	0.9600
C10—C11	1.383 (4)	C24—O3	1.421 (3)
C10—H10	0.9300	C24—H24A	0.9600
C11—C12	1.376 (5)	C24—H24B	0.9600
C11—H11	0.9300	C24—H24C	0.9600
C12—C13	1.370 (5)	N1—S1	1.6770 (19)
C12—H12	0.9300	O1—S1	1.4237 (19)
C13—C14	1.368 (4)	O2—S1	1.4269 (18)
C13—H13	0.9300

C6—C1—C2	121.5 (2)	C8—C15—H15	118.5
C6—C1—N1	107.75 (18)	C15—C16—C17	125.2 (2)
C2—C1—N1	130.7 (2)	C15—C16—H16	117.4
C3—C2—C1	117.2 (3)	C17—C16—H16	117.4
C3—C2—H2	121.4	C18—C17—C22	116.61 (19)
C1—C2—H2	121.4	C18—C17—C16	121.10 (18)
C4—C3—C2	121.8 (2)	C22—C17—C16	122.26 (19)
C4—C3—H3	119.1	C17—C18—C19	122.0 (2)
C2—C3—H3	119.1	C17—C18—H18	119.0
C3—C4—C5	121.4 (3)	C19—C18—H18	119.0
C3—C4—H4	119.3	O3—C19—C20	125.0 (2)
C5—C4—H4	119.3	O3—C19—C18	115.1 (2)
C4—C5—C6	118.3 (3)	C20—C19—C18	119.9 (2)
C4—C5—H5	120.9	C21—C20—C19	119.2 (2)
C6—C5—H5	120.9	C21—C20—H20	120.4
C1—C6—C5	119.8 (2)	C19—C20—H20	120.4
C1—C6—C7	108.3 (2)	C22—C21—C20	120.9 (2)
C5—C6—C7	131.8 (2)	C22—C21—H21	119.5
C8—C7—C6	108.00 (19)	C20—C21—H21	119.5
C8—C7—C23	128.0 (2)	C21—C22—C17	121.4 (2)
C6—C7—C23	123.7 (2)	C21—C22—Br1	117.89 (17)
C7—C8—N1	109.18 (18)	C17—C22—Br1	120.70 (17)
C7—C8—C15	128.9 (2)	C7—C23—H23A	109.5
N1—C8—C15	121.62 (19)	C7—C23—H23B	109.5
C10—C9—C14	120.9 (2)	H23A—C23—H23B	109.5
C10—C9—S1	119.18 (19)	C7—C23—H23C	109.5
C14—C9—S1	119.9 (2)	H23A—C23—H23C	109.5
C9—C10—C11	118.8 (3)	H23B—C23—H23C	109.5
C9—C10—H10	120.6	O3—C24—H24A	109.5
C11—C10—H10	120.6	O3—C24—H24B	109.5
C12—C11—C10	120.3 (3)	H24A—C24—H24B	109.5
C12—C11—H11	119.8	O3—C24—H24C	109.5
C10—C11—H11	119.8	H24A—C24—H24C	109.5
C13—C12—C11	120.0 (3)	H24B—C24—H24C	109.5
C13—C12—H12	120.0	C1—N1—C8	106.63 (17)
C11—C12—H12	120.0	C1—N1—S1	120.69 (15)
C14—C13—C12	120.7 (3)	C8—N1—S1	121.31 (15)
C14—C13—H13	119.7	C19—O3—C24	117.8 (2)
C12—C13—H13	119.7	O1—S1—O2	119.67 (12)
C13—C14—C9	119.3 (3)	O1—S1—N1	107.06 (10)
C13—C14—H14	120.4	O2—S1—N1	105.82 (11)
C9—C14—H14	120.4	O1—S1—C9	109.61 (12)
C16—C15—C8	122.9 (2)	O2—S1—C9	109.65 (12)
C16—C15—H15	118.5	N1—S1—C9	103.78 (10)

C6—C1—C2—C3	0.2 (4)	C17—C18—C19—O3	−179.1 (2)
N1—C1—C2—C3	178.4 (2)	C17—C18—C19—C20	1.2 (4)
C1—C2—C3—C4	−0.6 (4)	O3—C19—C20—C21	179.4 (2)
C2—C3—C4—C5	0.0 (4)	C18—C19—C20—C21	−0.9 (4)
C3—C4—C5—C6	0.8 (4)	C19—C20—C21—C22	−0.7 (4)
C2—C1—C6—C5	0.6 (3)	C20—C21—C22—C17	2.1 (4)
N1—C1—C6—C5	−177.9 (2)	C20—C21—C22—Br1	−177.9 (2)
C2—C1—C6—C7	179.6 (2)	C18—C17—C22—C21	−1.8 (3)
N1—C1—C6—C7	1.0 (2)	C16—C17—C22—C21	176.4 (2)
C4—C5—C6—C1	−1.1 (4)	C18—C17—C22—Br1	178.23 (15)
C4—C5—C6—C7	−179.8 (2)	C16—C17—C22—Br1	−3.6 (3)
C1—C6—C7—C8	1.2 (3)	C6—C1—N1—C8	−2.7 (2)
C5—C6—C7—C8	180.0 (3)	C2—C1—N1—C8	178.9 (2)
C1—C6—C7—C23	−173.6 (2)	C6—C1—N1—S1	−146.59 (16)
C5—C6—C7—C23	5.2 (4)	C2—C1—N1—S1	35.0 (3)
C6—C7—C8—N1	−2.9 (2)	C7—C8—N1—C1	3.5 (2)
C23—C7—C8—N1	171.6 (2)	C15—C8—N1—C1	177.77 (19)
C6—C7—C8—C15	−176.6 (2)	C7—C8—N1—S1	147.12 (16)
C23—C7—C8—C15	−2.1 (4)	C15—C8—N1—S1	−38.6 (3)
C14—C9—C10—C11	0.4 (4)	C20—C19—O3—C24	1.6 (4)
S1—C9—C10—C11	−177.1 (2)	C18—C19—O3—C24	−178.1 (3)
C9—C10—C11—C12	−0.1 (5)	C1—N1—S1—O1	−175.43 (16)
C10—C11—C12—C13	0.3 (5)	C8—N1—S1—O1	45.94 (19)
C11—C12—C13—C14	−0.8 (5)	C1—N1—S1—O2	−46.74 (19)
C12—C13—C14—C9	1.1 (4)	C8—N1—S1—O2	174.62 (17)
C10—C9—C14—C13	−0.9 (4)	C1—N1—S1—C9	68.69 (18)
S1—C9—C14—C13	176.6 (2)	C8—N1—S1—C9	−69.95 (18)
C7—C8—C15—C16	−45.2 (3)	C10—C9—S1—O1	−23.7 (2)
N1—C8—C15—C16	141.7 (2)	C14—C9—S1—O1	158.74 (19)
C8—C15—C16—C17	173.14 (19)	C10—C9—S1—O2	−157.0 (2)
C15—C16—C17—C18	−27.4 (3)	C14—C9—S1—O2	25.5 (2)
C15—C16—C17—C22	154.5 (2)	C10—C9—S1—N1	90.3 (2)
C22—C17—C18—C19	0.2 (3)	C14—C9—S1—N1	−87.2 (2)
C16—C17—C18—C19	−178.1 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.39	2.958 (4)	119
C3—H3···O2ⁱ	0.93	2.61	3.448 (3)	150
C24—H24A···Br1ⁱⁱ	0.96	3.03	3.699 (3)	128
C5—H5···Cg(C9–C14)ⁱⁱⁱ	0.93	3.12	4.047 (3)	173
C20—H20···Cg(C17–C22)^iv	0.93	3.15	3.978 (2)	149
C23—H23C···Cg(C1–C6)ⁱⁱⁱ	0.96	3.11	4.036 (4)	162

Symmetry codes: (i) −x+1, −y+1, −z; (ii) x−1, −y+1/2, z+1/2; (iii) −x+2, −y+1, −z+1; (iv) x, −y+1/2, z+1/2.

2-[(E)-2-(2-Bromophenyl)ethenyl]-3-methyl-1-(phenylsulfonyl)-1H-indole (III) top

Crystal data top

C₂₃H₁₈BrNO₂S	F(000) = 920
M_r = 452.35	D_x = 1.516 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 12.5530 (8) Å	Cell parameters from 50531 reflections
b = 8.3533 (5) Å	θ = 1.4–25.0°
c = 19.7698 (11) Å	µ = 2.20 mm⁻¹
β = 107.078 (2)°	T = 298 K
V = 1981.6 (2) Å³	Prism, yellow
Z = 4	0.36 × 0.31 × 0.24 mm

Data collection top

Bruker D8 Venture Diffractometer	3516 reflections with I > 2σ(I)
Radiation source: micro focus sealed tube	R_int = 0.058
ω and φ scans	θ_max = 27.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −16→16
T_min = 0.514, T_max = 0.745	k = −10→10
50531 measured reflections	l = −25→25
4293 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.036	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.10	w = 1/[σ²(F_o²) + (0.0262P)² + 1.371P] where P = (F_o² + 2F_c²)/3
4293 reflections	(Δ/σ)_max < 0.001
254 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Special details top

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.3845 (2)	0.7169 (3)	0.40613 (15)	0.0514 (6)
C2	0.2805 (2)	0.6430 (4)	0.3796 (2)	0.0725 (9)
H2	0.242636	0.642367	0.331512	0.087*
C3	0.2367 (3)	0.5708 (4)	0.4288 (3)	0.0861 (12)
H3	0.168029	0.519654	0.413097	0.103*
C4	0.2916 (3)	0.5724 (4)	0.5001 (3)	0.0847 (11)
H4	0.258724	0.524019	0.531342	0.102*
C5	0.3941 (3)	0.6443 (4)	0.52611 (19)	0.0691 (9)
H5	0.430809	0.644742	0.574390	0.083*
C6	0.4420 (2)	0.7169 (3)	0.47795 (15)	0.0510 (6)
C7	0.5465 (2)	0.7977 (3)	0.48800 (13)	0.0461 (6)
C8	0.55284 (19)	0.8444 (3)	0.42348 (13)	0.0430 (5)
C9	0.5022 (2)	0.5840 (3)	0.28233 (12)	0.0434 (5)
C10	0.6151 (2)	0.5774 (3)	0.28776 (13)	0.0516 (6)
H10	0.658022	0.670085	0.295131	0.062*
C11	0.6624 (3)	0.4304 (4)	0.28198 (15)	0.0618 (7)
H11	0.737661	0.423945	0.285032	0.074*
C12	0.5984 (3)	0.2933 (3)	0.27172 (14)	0.0627 (8)
H12	0.630690	0.194953	0.267756	0.075*
C13	0.4875 (3)	0.3010 (3)	0.26731 (15)	0.0609 (7)
H13	0.445370	0.207621	0.260770	0.073*
C14	0.4379 (2)	0.4461 (3)	0.27251 (13)	0.0532 (6)
H14	0.362668	0.451289	0.269471	0.064*
C15	0.6425 (2)	0.9296 (3)	0.40580 (12)	0.0443 (5)
H15	0.625141	1.018220	0.376123	0.053*
C16	0.7487 (2)	0.8842 (3)	0.43088 (12)	0.0425 (5)
H16	0.763379	0.793865	0.459639	0.051*
C17	0.84434 (19)	0.9639 (3)	0.41719 (11)	0.0393 (5)
C18	0.8460 (2)	1.1291 (3)	0.40596 (13)	0.0495 (6)
H18	0.784735	1.190395	0.407169	0.059*
C19	0.9364 (3)	1.2033 (3)	0.39313 (14)	0.0572 (7)
H19	0.934596	1.312866	0.384518	0.069*
C20	1.0296 (2)	1.1155 (3)	0.39303 (13)	0.0542 (7)
H20	1.091088	1.166316	0.385527	0.065*
C21	1.0315 (2)	0.9525 (3)	0.40404 (13)	0.0481 (6)
H21	1.093843	0.892468	0.403982	0.058*
C22	0.93913 (19)	0.8795 (3)	0.41520 (12)	0.0402 (5)
C23	0.6286 (3)	0.8304 (4)	0.55857 (14)	0.0608 (7)
H23A	0.670017	0.734729	0.575877	0.091*
H23B	0.589586	0.863969	0.591254	0.091*
H23C	0.678808	0.913412	0.553866	0.091*
N1	0.45078 (16)	0.8027 (2)	0.37072 (11)	0.0471 (5)
O1	0.50537 (19)	0.8925 (2)	0.26566 (10)	0.0640 (5)
O2	0.32416 (17)	0.7603 (3)	0.24957 (11)	0.0761 (6)
S1	0.44041 (6)	0.77168 (8)	0.28558 (3)	0.05103 (17)
Br1	0.94200 (2)	0.65291 (3)	0.42493 (2)	0.06143 (11)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0422 (13)	0.0425 (13)	0.0753 (18)	0.0112 (11)	0.0262 (13)	−0.0021 (12)
C2	0.0454 (15)	0.0663 (19)	0.107 (3)	0.0057 (14)	0.0239 (16)	−0.0137 (18)
C3	0.0554 (19)	0.062 (2)	0.160 (4)	−0.0014 (16)	0.061 (2)	−0.016 (2)
C4	0.089 (3)	0.058 (2)	0.138 (3)	0.0023 (18)	0.081 (3)	−0.005 (2)
C5	0.083 (2)	0.0539 (17)	0.091 (2)	0.0117 (16)	0.0584 (19)	0.0018 (15)
C6	0.0539 (15)	0.0407 (13)	0.0676 (17)	0.0137 (11)	0.0325 (13)	−0.0012 (12)
C7	0.0487 (14)	0.0398 (12)	0.0535 (14)	0.0145 (10)	0.0210 (11)	−0.0012 (11)
C8	0.0400 (12)	0.0379 (12)	0.0511 (13)	0.0111 (10)	0.0132 (10)	−0.0019 (10)
C9	0.0505 (14)	0.0375 (12)	0.0391 (12)	0.0021 (10)	0.0084 (10)	0.0030 (10)
C10	0.0521 (15)	0.0474 (14)	0.0529 (14)	−0.0001 (12)	0.0119 (12)	−0.0011 (12)
C11	0.0604 (17)	0.0616 (18)	0.0611 (17)	0.0177 (14)	0.0144 (13)	0.0008 (14)
C12	0.089 (2)	0.0433 (14)	0.0501 (15)	0.0187 (15)	0.0120 (15)	0.0001 (12)
C13	0.082 (2)	0.0415 (14)	0.0544 (16)	−0.0062 (14)	0.0129 (14)	−0.0009 (12)
C14	0.0561 (15)	0.0474 (15)	0.0535 (15)	−0.0034 (12)	0.0121 (12)	0.0005 (12)
C15	0.0483 (13)	0.0368 (12)	0.0478 (13)	0.0047 (10)	0.0145 (11)	0.0008 (10)
C16	0.0476 (13)	0.0362 (12)	0.0466 (13)	0.0064 (10)	0.0184 (11)	0.0002 (10)
C17	0.0448 (12)	0.0352 (11)	0.0375 (11)	0.0030 (9)	0.0117 (10)	−0.0026 (9)
C18	0.0584 (15)	0.0349 (12)	0.0540 (14)	0.0069 (11)	0.0148 (12)	−0.0014 (10)
C19	0.0750 (19)	0.0367 (13)	0.0567 (16)	−0.0078 (13)	0.0143 (14)	0.0024 (12)
C20	0.0537 (15)	0.0590 (17)	0.0484 (14)	−0.0158 (13)	0.0125 (12)	0.0007 (12)
C21	0.0423 (13)	0.0546 (15)	0.0479 (13)	0.0003 (11)	0.0139 (11)	−0.0029 (11)
C22	0.0458 (12)	0.0322 (11)	0.0419 (12)	0.0032 (9)	0.0115 (10)	−0.0017 (9)
C23	0.0679 (18)	0.0654 (18)	0.0511 (15)	0.0178 (14)	0.0204 (13)	−0.0022 (13)
N1	0.0404 (11)	0.0441 (11)	0.0564 (12)	0.0075 (9)	0.0134 (9)	−0.0016 (9)
O1	0.0944 (15)	0.0394 (10)	0.0564 (11)	0.0035 (10)	0.0194 (10)	0.0085 (8)
O2	0.0572 (12)	0.0791 (15)	0.0734 (13)	0.0209 (11)	−0.0100 (10)	−0.0017 (11)
S1	0.0548 (4)	0.0413 (3)	0.0503 (3)	0.0116 (3)	0.0049 (3)	0.0037 (3)
Br1	0.05484 (17)	0.03621 (14)	0.0976 (2)	0.00739 (11)	0.02920 (15)	−0.00128 (13)

Geometric parameters (Å, º) top

C1—C6	1.391 (4)	C13—C14	1.380 (4)
C1—C2	1.399 (4)	C13—H13	0.9300
C1—N1	1.428 (3)	C14—H14	0.9300
C2—C3	1.388 (5)	C15—C16	1.333 (3)
C2—H2	0.9300	C15—H15	0.9300
C3—C4	1.374 (5)	C16—C17	1.466 (3)
C3—H3	0.9300	C16—H16	0.9300
C4—C5	1.376 (5)	C17—C22	1.394 (3)
C4—H4	0.9300	C17—C18	1.399 (3)
C5—C6	1.404 (4)	C18—C19	1.381 (4)
C5—H5	0.9300	C18—H18	0.9300
C6—C7	1.437 (4)	C19—C20	1.381 (4)
C7—C8	1.358 (3)	C19—H19	0.9300
C7—C23	1.496 (4)	C20—C21	1.378 (4)
C8—N1	1.437 (3)	C20—H20	0.9300
C8—C15	1.458 (3)	C21—C22	1.383 (3)
C9—C14	1.387 (4)	C21—H21	0.9300
C9—C10	1.390 (4)	C22—Br1	1.902 (2)
C9—S1	1.759 (2)	C23—H23A	0.9600
C10—C11	1.383 (4)	C23—H23B	0.9600
C10—H10	0.9300	C23—H23C	0.9600
C11—C12	1.379 (4)	N1—S1	1.670 (2)
C11—H11	0.9300	O1—S1	1.424 (2)
C12—C13	1.370 (4)	O2—S1	1.427 (2)
C12—H12	0.9300

C6—C1—C2	122.0 (3)	C9—C14—H14	120.6
C6—C1—N1	107.3 (2)	C16—C15—C8	122.0 (2)
C2—C1—N1	130.7 (3)	C16—C15—H15	119.0
C3—C2—C1	116.5 (3)	C8—C15—H15	119.0
C3—C2—H2	121.7	C15—C16—C17	125.8 (2)
C1—C2—H2	121.7	C15—C16—H16	117.1
C4—C3—C2	122.1 (3)	C17—C16—H16	117.1
C4—C3—H3	118.9	C22—C17—C18	116.2 (2)
C2—C3—H3	118.9	C22—C17—C16	121.9 (2)
C3—C4—C5	121.3 (3)	C18—C17—C16	121.9 (2)
C3—C4—H4	119.3	C19—C18—C17	121.6 (2)
C5—C4—H4	119.3	C19—C18—H18	119.2
C4—C5—C6	118.3 (3)	C17—C18—H18	119.2
C4—C5—H5	120.8	C18—C19—C20	120.3 (2)
C6—C5—H5	120.8	C18—C19—H19	119.9
C1—C6—C5	119.6 (3)	C20—C19—H19	119.9
C1—C6—C7	108.7 (2)	C21—C20—C19	120.0 (3)
C5—C6—C7	131.7 (3)	C21—C20—H20	120.0
C8—C7—C6	107.9 (2)	C19—C20—H20	120.0
C8—C7—C23	127.5 (3)	C20—C21—C22	119.0 (2)
C6—C7—C23	124.4 (2)	C20—C21—H21	120.5
C7—C8—N1	109.1 (2)	C22—C21—H21	120.5
C7—C8—C15	128.9 (2)	C21—C22—C17	123.0 (2)
N1—C8—C15	122.0 (2)	C21—C22—Br1	117.57 (18)
C14—C9—C10	121.0 (2)	C17—C22—Br1	119.44 (17)
C14—C9—S1	120.0 (2)	C7—C23—H23A	109.5
C10—C9—S1	118.91 (19)	C7—C23—H23B	109.5
C11—C10—C9	118.8 (3)	H23A—C23—H23B	109.5
C11—C10—H10	120.6	C7—C23—H23C	109.5
C9—C10—H10	120.6	H23A—C23—H23C	109.5
C12—C11—C10	120.2 (3)	H23B—C23—H23C	109.5
C12—C11—H11	119.9	C1—N1—C8	106.8 (2)
C10—C11—H11	119.9	C1—N1—S1	122.15 (18)
C13—C12—C11	120.5 (3)	C8—N1—S1	123.93 (17)
C13—C12—H12	119.7	O1—S1—O2	119.60 (13)
C11—C12—H12	119.7	O1—S1—N1	106.70 (11)
C12—C13—C14	120.5 (3)	O2—S1—N1	106.19 (12)
C12—C13—H13	119.7	O1—S1—C9	109.10 (12)
C14—C13—H13	119.7	O2—S1—C9	108.67 (13)
C13—C14—C9	118.9 (3)	N1—S1—C9	105.70 (10)
C13—C14—H14	120.6

C6—C1—C2—C3	0.6 (4)	C22—C17—C18—C19	0.5 (4)
N1—C1—C2—C3	−178.8 (3)	C16—C17—C18—C19	180.0 (2)
C1—C2—C3—C4	0.6 (5)	C17—C18—C19—C20	−1.8 (4)
C2—C3—C4—C5	−1.0 (5)	C18—C19—C20—C21	1.6 (4)
C3—C4—C5—C6	0.1 (5)	C19—C20—C21—C22	−0.1 (4)
C2—C1—C6—C5	−1.5 (4)	C20—C21—C22—C17	−1.3 (4)
N1—C1—C6—C5	178.1 (2)	C20—C21—C22—Br1	176.59 (19)
C2—C1—C6—C7	178.4 (2)	C18—C17—C22—C21	1.1 (3)
N1—C1—C6—C7	−2.0 (3)	C16—C17—C22—C21	−178.4 (2)
C4—C5—C6—C1	1.1 (4)	C18—C17—C22—Br1	−176.75 (17)
C4—C5—C6—C7	−178.8 (3)	C16—C17—C22—Br1	3.7 (3)
C1—C6—C7—C8	−0.6 (3)	C6—C1—N1—C8	3.7 (2)
C5—C6—C7—C8	179.3 (3)	C2—C1—N1—C8	−176.8 (3)
C1—C6—C7—C23	176.2 (2)	C6—C1—N1—S1	155.22 (17)
C5—C6—C7—C23	−3.8 (4)	C2—C1—N1—S1	−25.3 (4)
C6—C7—C8—N1	3.0 (3)	C7—C8—N1—C1	−4.2 (2)
C23—C7—C8—N1	−173.7 (2)	C15—C8—N1—C1	178.2 (2)
C6—C7—C8—C15	−179.6 (2)	C7—C8—N1—S1	−155.05 (17)
C23—C7—C8—C15	3.7 (4)	C15—C8—N1—S1	27.3 (3)
C14—C9—C10—C11	1.1 (4)	C1—N1—S1—O1	171.57 (19)
S1—C9—C10—C11	−177.1 (2)	C8—N1—S1—O1	−41.8 (2)
C9—C10—C11—C12	−0.6 (4)	C1—N1—S1—O2	42.9 (2)
C10—C11—C12—C13	−0.2 (4)	C8—N1—S1—O2	−170.45 (19)
C11—C12—C13—C14	0.5 (4)	C1—N1—S1—C9	−72.4 (2)
C12—C13—C14—C9	−0.1 (4)	C8—N1—S1—C9	74.2 (2)
C10—C9—C14—C13	−0.7 (4)	C14—C9—S1—O1	−155.3 (2)
S1—C9—C14—C13	177.4 (2)	C10—C9—S1—O1	22.9 (2)
C7—C8—C15—C16	48.7 (4)	C14—C9—S1—O2	−23.3 (2)
N1—C8—C15—C16	−134.1 (2)	C10—C9—S1—O2	154.9 (2)
C8—C15—C16—C17	−178.7 (2)	C14—C9—S1—N1	90.3 (2)
C15—C16—C17—C22	−149.4 (2)	C10—C9—S1—N1	−91.5 (2)
C15—C16—C17—C18	31.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O2	0.93	2.37	2.949 (5)	120
C13—H13···O1ⁱ	0.93	2.73	3.420 (3)	132
C14—H14···O2ⁱⁱ	0.93	2.77	3.547 (4)	142
C19—H19···Br1ⁱⁱⁱ	0.93	2.94	3.805 (3)	155
C5—H5···Cg(C9–C14)^iv	0.93	2.96	3.806 (4)	153
C23—H23A···Cg(C1–C6)^iv	0.96	3.21	3.999 (3)	110
C23—H23B···Cg(N1/C1/C6–C8)^v	0.96	3.12	3.561 (3)	149

Symmetry codes: (i) x, y−1, z; (ii) −x+1/2, y−1/2, −z+1/2; (iii) x, y+1, z; (iv) −x+1, −y+1, −z+1; (v) −x+1, −y+2, −z+1.

Geometry of stacking interactions (Å, °) for I–III top

Cg is a group centroid; Plane···CgB is the distance between the mean plane of Group A and the centroid of the interacting Group B; ipa is the interplanar angle; sa is the slippage angle, which is the angle of the CgA···CgB axis to the Group A mean plane normal.

Compound	Group A	Group B	Shortest contacts	CgA···CgB	Plane···CgB	ipa	sa
I	(N1/C1–C8)	(N1/C1–C8)ⁱⁱⁱ	3.573 (4)	3.628 (2)	3.551 (2)	0	11.8 (2)
	(N1/C1–C8)	(C1–C6)ⁱⁱⁱ	3.573 (4)	3.831 (2)	3.552 (2)	0.16 (14)	22.0 (2)
II	(N1/C1–C8)	(N1/C1–C8)^v	3.618 (3)	3.692 (2)	3.633 (2)	0	10.3 (2)
	(N1/C1–C8)	(C1–C6)^v	3.618 (3)	3.975 (2)	3.635 (2)	0.62 (13)	23.9 (2)
	(C17–C22)	(C19–C14)^vii	3.463 (3)	3.836 (3)	3.646 (3)	9.56 (16)	18.1 (2)
III	(C17–C22)	(C9–C14)^vi	3.381 (3)	3.742 (2)	3.379 (2)	10.34 (7)	24.5 (2)
	(C17–C22)	(C17–C22)^vii	3.489 (3)	3.691 (2)	3.488 (2)	0	19.1 (2)

Symmetry codes for I: (iii) -x + 1, -y + 1, -z + 1; for II: (v) -x + 1, -y + 1, -z + 1; (vii) x, y, z - 1; for III: (vi) -x + 3/2, y + 1/2, -z + 1/2; (vii) -x + 2, -y + 2, -z + 1.

Calculated interaction energies (kJ mol^-1) for I–III top

Interaction energies were calculated employing the CE-B3LYP/6-31G(d,p) functional/basis set combination. The scale factors used to determine E_tot were: k_ele = 1.057, k_pol = 0.740, k_dis = 0.871, and k_rep = 0.618 (Mackenzie et al., 2017). For details of the interaction modes, see Figs. 8–10; R is the distance in Å between the centroids of interacting molecules.

Type	Symmetry code	Interaction	R	E_ele	E_pol	E_dis	E_rep	E_tot
Compound I
A	-x + 1, -y + 1, -z + 1	π–π, CH···O	6.45	-20.2	-4.5	-71.5	42.4	-60.8
B	-x, -y + 1, -z + 1	CH–π	6.35	-10.5	-2.0	-59.9	32.8	-44.4
C	-x + 1, y - 1/2, -z + 3/2	CH···O	7.79	-7.9	-3.6	-22.8	14.0	-22.2
D	x - 1, y, z	CH···O	7.98	-5.7	-2.0	-10.6	6.0	-13.1
E	x, -y + 3/2, z - 1/2	CH···Br, CH···π	9.09	-5.0	-0.9	-18.6	10.4	-15.7
F	-x, y - 1/2, -z + 3/2	CH···Br	9.03	-2.3	-1.0	-17.8	8.5	-13.4
Compound II
A	-x + 1, -y + 1, -z + 1	π–π	8.08	-8.9	-2.9	-67.3	29.0	-52.3
B	-x + 2, -y + 1, -z + 1	CH—π	8.10	-15.7	-1.7	-67.9	44.6	-49.4
C	-x+1, -y+1, -z	CH···O	12.70	-12.6	-2.9	-15.4	0.0	-28.9
D	x + 1, y, z	CH···O	8.43	-7.1	-2.2	-18.7	13.6	-17.1
E	x, y, z - 1	π–π	8.95	-4.2	-2.6	-47.8	22.8	-33.9
F	x, -y + 1/2, z - 1/2	CH···Br, CH···π	8.77	-6.2	-2.2	-38.6	20.2	-29.3
Compound III
A	-x + 1, -y + 1, -z + 1	CH···π, dispersion	7.64	-11.5	-1.9	-78.4	43.3	-55.1
B	-x + 1, -y + 2, -z + 1	CH···π	7.91	-9.3	-2.0	-57.5	29.5	-43.1
C	-x + 3/2, y + 1/2, -z + 1/2	π–π	7.85	-7.1	-1.7	-40.7	21.3	-31.0
D	-x + 2, -y + 2, -z + 1	π–π	9.91	-5.2	-1.1	-50.4	34.5	-28.9
E	x, y - 1, z	CH···O, CH···Br	8.35	-10.5	-2.7	-28.3	21.7	-24.3
F	-x + 1/2, y - 1/2, -z + 1/2	CH···O	10.52	-3.6	-2.7	-15.6	6.0	-15.7

Acknowledgements

The authors thanks to the SAIF, IIT, Madras, India, for the data collection.

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research communications\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

1. Chemical context

2. Structural commentary

3. Supra­molecular features

4. Hirshfeld surface analysis

5. Database survey

6. Synthesis and crystallization

7. Refinement

Supporting information

Acknowledgements

References

research communications

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

3. Supramolecular features