3-Iodo-2-methyl-1-phenyl­sulfonyl-1H-indole

Ramathilagam, C.; Saravanan, V.; Mohanakrishnan, A.K.; Chakkaravarthi, G.; Umarani, P.R.; Manivannan, V.

doi:10.1107/S1600536811004685

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o632

doi:10.1107/S1600536811004685

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3-Iodo-2-methyl-1-phenylsulfonyl-1H-indole

C. Ramathilagam,^a Velu Saravanan,^b A. K. Mohanakrishnan,^b G. Chakkaravarthi,^c P. R. Umarani ^d and V. Manivannan ^e ^*

^aDepartment of Physics, AMET University, Kanathur, Chennai 603 112, India, ^bDepartment of Organic Chemistry, University of Madras, Guindy Campus, Chennai 600 025, India, ^cDepartment of Physics, CPCL Polytechnic College, Chennai 600 068, India, ^dDepartment of Physics, Presidency College (Autonomous), Chennai 600 005, India, and ^eDepartment of Research and Development, PRIST University, Vallam, Thanjavur 613 403, Tamil Nadu, India
^*Correspondence e-mail: crystallography2010@gmail.com, chakkaravarthi_2005@yahoo.com

(Received 31 January 2011; accepted 7 February 2011; online 12 February 2011)

In the title compound, C₁₅H₁₂INO₂S, the sulfonyl-bound phenyl ring forms a dihedral angle 82.84 (9)° with the indole ring system. The molecular structure is stabilized by a weak intramolecular C—H⋯O hydrogen bond. The crystal structure exhibits weak intermolecular C—H⋯π interactions and π–π interactions between the indole groups [centroid–centroid distance between the five-membered and six-membered rings of the indole group = 3.7617 (18) Å].

Related literature

For the biological properties of indole derivatives, see: Chai et al. (2006 ); Nieto et al. (2005 ). For the structures of closely related compounds, see: Chakkaravarthi et al. (2007 , 2008 ).

Experimental

Crystal data

C₁₅H₁₂INO₂S
M_r = 397.22
Monoclinic, P 2₁ /c
a = 10.7068 (3) Å
b = 16.2670 (4) Å
c = 8.5147 (2) Å
β = 104.540 (1)°
V = 1435.49 (6) Å³
Z = 4
Mo Kα radiation
μ = 2.38 mm⁻¹
T = 295 K
0.30 × 0.24 × 0.20 mm

Data collection

Bruker Kappa APEXII diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.536, T_max = 0.648
21249 measured reflections
5276 independent reflections
3696 reflections with I > 2σ(I)
R_int = 0.023

Refinement

R[F² > 2σ(F²)] = 0.043
wR(F²) = 0.144
S = 1.06
5276 reflections
182 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −1.56 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg3 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O1	0.93	2.29	2.871 (4)	120
C4—H4⋯Cg3ⁱ	0.93	2.65	3.517 (5)	156
Symmetry code: (i) -x+2, -y, -z+2.

Data collection: APEX2 (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811004685/gk2346sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811004685/gk2346Isup2.hkl

checkCIF report

Comment top

Indole derivatives exhibit antihepatitis B virus (Chai et al., 2006) and antibacterial (Nieto et al., 2005) activities. The geometric parameters of the title molecule (Fig. 1) agree well with the reported similar structures (Chakkaravarthi et al. 2007, 2008).

The phenyl ring makes the dihedral angle of 82.84 (9)° with the indole ring system. The sum of the bond angles around N1 [359.4 (2)°] indicates that N1 atom is sp² hybridized. The molecular structure is stabilized by weak intramolecular C—H···O hydrogen bond. The crystal structure exhibits weak intermolecular C—H···π (Table 1) and π–π interactions [Cg1···Cg3 (1 - x,-y,1 - z) 3.7617 (18) Å; Cg1 and Cg3 are the centroids of the rings N1/C7/C8/C9/C14 and C9—C14, respectively].

Related literature top

For the biological properties of indole derivatives, see: Chai et al. (2006); Nieto et al. (2005). For the structures of closely related compounds, see: Chakkaravarthi et al. (2007, 2008).

Experimental top

3-Iodo-2-methylindole (5 g,0.02 mmole) was dissolved in distilled benzene (100 ml).To this, benzenesulfonyl chloride(3.23 ml,0.025 mmol) and 60% aqueous NaOH solution (40 g in 67.0 ml) were added along with tetrabutyl ammonium hydrogensulfate (1.0 g). This two phase system was stirred at room temperature for 2 h. It was then diluted with water (200 ml) and the organic layer was separated. The aqueous layer was extracted with benzene (2x20 ml). The combined organic layer was dried(Na₂SO₄).The benzene was then removed completely and the crude product was recrystallized from methanol (m.p. 395–397 K).

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Crystal packing viewed along the b axis.

3-Iodo-2-methyl-1-phenylsulfonyl-1H-indole top

Crystal data top

C₁₅H₁₂INO₂S	F(000) = 776
M_r = 397.22	D_x = 1.838 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8510 reflections
a = 10.7068 (3) Å	θ = 2.5–30.4°
b = 16.2670 (4) Å	µ = 2.38 mm⁻¹
c = 8.5147 (2) Å	T = 295 K
β = 104.540 (1)°	Block, colourless
V = 1435.49 (6) Å³	0.30 × 0.24 × 0.20 mm
Z = 4

Data collection top

Bruker Kappa APEXII diffractometer	5276 independent reflections
Radiation source: fine-focus sealed tube	3696 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ω and ϕ scans	θ_max = 32.8°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −15→16
T_min = 0.536, T_max = 0.648	k = −23→24
21249 measured reflections	l = −12→11

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.144	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0743P)² + 0.987P] where P = (F_o² + 2F_c²)/3
5276 reflections	(Δ/σ)_max < 0.001
182 parameters	Δρ_max = 0.94 e Å⁻³
1 restraint	Δρ_min = −1.56 e Å⁻³

Crystal data top

C₁₅H₁₂INO₂S	V = 1435.49 (6) Å³
M_r = 397.22	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.7068 (3) Å	µ = 2.38 mm⁻¹
b = 16.2670 (4) Å	T = 295 K
c = 8.5147 (2) Å	0.30 × 0.24 × 0.20 mm
β = 104.540 (1)°

Data collection top

Bruker Kappa APEXII diffractometer	5276 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	3696 reflections with I > 2σ(I)
T_min = 0.536, T_max = 0.648	R_int = 0.023
21249 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	1 restraint
wR(F²) = 0.144	H-atom parameters constrained
S = 1.06	Δρ_max = 0.94 e Å⁻³
5276 reflections	Δρ_min = −1.56 e Å⁻³
182 parameters

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

	x	y	z	U_iso*/U_eq
C1	0.8489 (3)	0.14775 (16)	0.8788 (3)	0.0350 (5)
C2	0.8848 (4)	0.0951 (2)	1.0097 (4)	0.0495 (7)
H2	0.8265	0.0574	1.0324	0.059*
C3	1.0098 (4)	0.0998 (3)	1.1063 (5)	0.0638 (10)
H3	1.0365	0.0646	1.1944	0.077*
C4	1.0940 (4)	0.1562 (3)	1.0722 (5)	0.0643 (11)
H4	1.1778	0.1587	1.1375	0.077*
C5	1.0569 (3)	0.2092 (3)	0.9431 (5)	0.0556 (9)
H5	1.1149	0.2478	0.9227	0.067*
C6	0.9331 (3)	0.20492 (19)	0.8436 (4)	0.0433 (6)
H6	0.9073	0.2398	0.7549	0.052*
C7	0.7397 (3)	0.04833 (16)	0.5161 (3)	0.0329 (5)
C8	0.7262 (3)	−0.03190 (16)	0.4724 (3)	0.0336 (5)
C9	0.6619 (2)	−0.07527 (14)	0.5739 (3)	0.0297 (4)
C10	0.6230 (3)	−0.15718 (17)	0.5777 (4)	0.0387 (6)
H10	0.6379	−0.1950	0.5025	0.046*
C11	0.5626 (3)	−0.1805 (2)	0.6940 (4)	0.0478 (7)
H11	0.5362	−0.2348	0.6978	0.057*
C12	0.5402 (3)	−0.1249 (2)	0.8061 (4)	0.0486 (7)
H12	0.5005	−0.1429	0.8852	0.058*
C13	0.5753 (3)	−0.0428 (2)	0.8043 (4)	0.0435 (6)
H13	0.5585	−0.0055	0.8792	0.052*
C14	0.6367 (2)	−0.01869 (15)	0.6857 (3)	0.0309 (5)
C15	0.7993 (4)	0.1168 (2)	0.4432 (5)	0.0509 (7)
H15A	0.8230	0.0972	0.3483	0.076*
H15B	0.8748	0.1362	0.5208	0.076*
H15C	0.7383	0.1609	0.4137	0.076*
N1	0.6822 (2)	0.05838 (13)	0.6481 (3)	0.0335 (4)
O1	0.6046 (2)	0.13114 (15)	0.8577 (4)	0.0552 (6)
O2	0.6719 (2)	0.21172 (13)	0.6496 (3)	0.0533 (6)
S1	0.68958 (6)	0.14402 (4)	0.75748 (10)	0.03797 (16)
I1	0.78752 (3)	−0.084909 (16)	0.28650 (3)	0.06383 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0355 (12)	0.0307 (11)	0.0379 (13)	0.0043 (9)	0.0078 (10)	−0.0078 (10)
C2	0.0583 (19)	0.0487 (17)	0.0391 (15)	0.0014 (14)	0.0076 (14)	0.0020 (12)
C3	0.071 (3)	0.070 (2)	0.0421 (18)	0.020 (2)	−0.0008 (17)	0.0018 (17)
C4	0.0421 (17)	0.087 (3)	0.056 (2)	0.0121 (17)	−0.0013 (15)	−0.025 (2)
C5	0.0409 (16)	0.065 (2)	0.061 (2)	−0.0088 (14)	0.0131 (14)	−0.0205 (18)
C6	0.0436 (15)	0.0406 (14)	0.0458 (15)	−0.0039 (11)	0.0117 (12)	−0.0062 (12)
C7	0.0368 (12)	0.0290 (11)	0.0337 (12)	−0.0026 (9)	0.0107 (9)	0.0026 (9)
C8	0.0411 (13)	0.0293 (11)	0.0303 (11)	−0.0013 (9)	0.0088 (9)	0.0012 (8)
C9	0.0297 (11)	0.0280 (11)	0.0287 (11)	−0.0016 (8)	0.0025 (8)	0.0014 (8)
C10	0.0444 (14)	0.0295 (12)	0.0376 (13)	−0.0067 (10)	0.0021 (11)	−0.0005 (10)
C11	0.0440 (15)	0.0395 (15)	0.0552 (17)	−0.0157 (12)	0.0036 (13)	0.0100 (13)
C12	0.0407 (15)	0.0578 (19)	0.0489 (17)	−0.0109 (13)	0.0143 (12)	0.0130 (15)
C13	0.0415 (14)	0.0501 (16)	0.0427 (15)	−0.0046 (12)	0.0178 (12)	0.0006 (12)
C14	0.0272 (10)	0.0321 (11)	0.0326 (11)	−0.0008 (8)	0.0058 (9)	0.0005 (9)
C15	0.064 (2)	0.0396 (15)	0.0548 (18)	−0.0110 (14)	0.0261 (15)	0.0073 (14)
N1	0.0389 (11)	0.0255 (9)	0.0373 (11)	−0.0027 (8)	0.0120 (9)	−0.0033 (8)
O1	0.0433 (11)	0.0543 (13)	0.0750 (17)	0.0013 (10)	0.0278 (11)	−0.0227 (12)
O2	0.0528 (13)	0.0308 (10)	0.0659 (15)	0.0113 (9)	−0.0047 (11)	0.0013 (10)
S1	0.0335 (3)	0.0299 (3)	0.0491 (4)	0.0048 (2)	0.0078 (3)	−0.0079 (3)
I1	0.0954 (2)	0.05448 (17)	0.05233 (17)	0.00090 (11)	0.03859 (15)	−0.00527 (9)

Geometric parameters (Å, º) top

C1—C6	1.380 (4)	C9—C14	1.399 (4)
C1—C2	1.381 (4)	C9—C10	1.399 (3)
C1—S1	1.759 (3)	C10—C11	1.365 (5)
C2—C3	1.386 (6)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.379 (5)
C3—C4	1.367 (7)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.387 (5)
C4—C5	1.375 (6)	C12—H12	0.9300
C4—H4	0.9300	C13—C14	1.392 (4)
C5—C6	1.384 (5)	C13—H13	0.9300
C5—H5	0.9300	C14—N1	1.411 (3)
C6—H6	0.9300	C15—H15A	0.9600
C7—C8	1.355 (4)	C15—H15B	0.9600
C7—N1	1.420 (3)	C15—H15C	0.9600
C7—C15	1.493 (4)	N1—S1	1.667 (2)
C8—C9	1.421 (4)	O1—S1	1.411 (3)
C8—I1	2.050 (3)	O2—S1	1.416 (3)

C6—C1—C2	121.9 (3)	C9—C10—H10	120.7
C6—C1—S1	119.1 (2)	C10—C11—C12	121.0 (3)
C2—C1—S1	119.0 (2)	C10—C11—H11	119.5
C1—C2—C3	118.5 (4)	C12—C11—H11	119.5
C1—C2—H2	120.8	C11—C12—C13	122.0 (3)
C3—C2—H2	120.8	C11—C12—H12	119.0
C4—C3—C2	120.0 (4)	C13—C12—H12	119.0
C4—C3—H3	120.0	C12—C13—C14	117.2 (3)
C2—C3—H3	120.0	C12—C13—H13	121.4
C3—C4—C5	121.1 (3)	C14—C13—H13	121.4
C3—C4—H4	119.4	C13—C14—C9	121.0 (2)
C5—C4—H4	119.4	C13—C14—N1	132.0 (3)
C4—C5—C6	119.9 (4)	C9—C14—N1	107.0 (2)
C4—C5—H5	120.0	C7—C15—H15A	109.5
C6—C5—H5	120.0	C7—C15—H15B	109.5
C1—C6—C5	118.6 (3)	H15A—C15—H15B	109.5
C1—C6—H6	120.7	C7—C15—H15C	109.5
C5—C6—H6	120.7	H15A—C15—H15C	109.5
C8—C7—N1	106.9 (2)	H15B—C15—H15C	109.5
C8—C7—C15	129.1 (3)	C14—N1—C7	108.7 (2)
N1—C7—C15	123.9 (3)	C14—N1—S1	125.89 (19)
C7—C8—C9	110.2 (2)	C7—N1—S1	124.72 (18)
C7—C8—I1	125.8 (2)	O1—S1—O2	120.43 (16)
C9—C8—I1	124.00 (18)	O1—S1—N1	105.47 (13)
C14—C9—C10	120.1 (2)	O2—S1—N1	107.93 (14)
C14—C9—C8	107.1 (2)	O1—S1—C1	109.09 (15)
C10—C9—C8	132.8 (3)	O2—S1—C1	107.83 (14)
C11—C10—C9	118.7 (3)	N1—S1—C1	105.06 (12)
C11—C10—H10	120.7

C6—C1—C2—C3	−0.7 (5)	C8—C9—C14—C13	−179.2 (3)
S1—C1—C2—C3	−178.7 (3)	C10—C9—C14—N1	−177.8 (2)
C1—C2—C3—C4	0.7 (6)	C8—C9—C14—N1	1.6 (3)
C2—C3—C4—C5	0.3 (6)	C13—C14—N1—C7	179.0 (3)
C3—C4—C5—C6	−1.1 (6)	C9—C14—N1—C7	−2.0 (3)
C2—C1—C6—C5	−0.1 (5)	C13—C14—N1—S1	8.1 (4)
S1—C1—C6—C5	177.9 (2)	C9—C14—N1—S1	−172.91 (19)
C4—C5—C6—C1	1.0 (5)	C8—C7—N1—C14	1.6 (3)
N1—C7—C8—C9	−0.5 (3)	C15—C7—N1—C14	−179.7 (3)
C15—C7—C8—C9	−179.2 (3)	C8—C7—N1—S1	172.6 (2)
N1—C7—C8—I1	179.13 (18)	C15—C7—N1—S1	−8.7 (4)
C15—C7—C8—I1	0.5 (5)	C14—N1—S1—O1	−19.0 (3)
C7—C8—C9—C14	−0.7 (3)	C7—N1—S1—O1	171.5 (2)
I1—C8—C9—C14	179.62 (18)	C14—N1—S1—O2	−149.0 (2)
C7—C8—C9—C10	178.6 (3)	C7—N1—S1—O2	41.5 (3)
I1—C8—C9—C10	−1.1 (4)	C14—N1—S1—C1	96.2 (2)
C14—C9—C10—C11	−1.3 (4)	C7—N1—S1—C1	−73.3 (2)
C8—C9—C10—C11	179.5 (3)	C6—C1—S1—O1	−139.6 (2)
C9—C10—C11—C12	0.0 (5)	C2—C1—S1—O1	38.4 (3)
C10—C11—C12—C13	1.3 (5)	C6—C1—S1—O2	−7.2 (3)
C11—C12—C13—C14	−1.1 (5)	C2—C1—S1—O2	170.8 (3)
C12—C13—C14—C9	−0.2 (4)	C6—C1—S1—N1	107.7 (2)
C12—C13—C14—N1	178.7 (3)	C2—C1—S1—N1	−74.2 (3)
C10—C9—C14—C13	1.4 (4)

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1	0.93	2.29	2.871 (4)	120
C4—H4···Cg3ⁱ	0.93	2.65	3.517 (5)	156

Symmetry code: (i) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₂INO₂S
M_r	397.22
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	10.7068 (3), 16.2670 (4), 8.5147 (2)
β (°)	104.540 (1)
V (Å³)	1435.49 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.38
Crystal size (mm)	0.30 × 0.24 × 0.20

Data collection
Diffractometer	Bruker Kappa APEXII diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.536, 0.648
No. of measured, independent and observed [I > 2σ(I)] reflections	21249, 5276, 3696
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.761

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.144, 1.06
No. of reflections	5276
No. of parameters	182
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −1.56

Computer programs: APEX2 (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg3 is the centroid of the C9–C14 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O1	0.93	2.29	2.871 (4)	120
C4—H4···Cg3ⁱ	0.93	2.65	3.517 (5)	156

Symmetry code: (i) −x+2, −y, −z+2.

Acknowledgements

CR wishes to acknowledge AMET University management, India, for their kind support.

References

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Volume 67| Part 3| March 2011| Page o632

doi:10.1107/S1600536811004685

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