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Acta Crystallogr Sect E Struct Rep Online. 2008 April 1; 64(Pt 4): o732.
Published online 2008 March 20. doi:  10.1107/S1600536808007319
PMCID: PMC2960959

Ethyl 2-(bromo­meth­yl)-5-meth­oxy-1-phenyl­sulfonyl-1H-indole-3-carboxyl­ate

Abstract

In the title compound, C19H18BrNO5S, the plane of the phenyl ring forms a dihedral angle of 76.99 (6)° with the indole ring system. The Br atom is disordered over two positions, with site-occupancy factors of 0.833 (14) and 0.167 (14). The mol­ecular structure is stabilized by weak intra­molecular C—H(...)O inter­actions and the crystal packing is stabilized by weak inter­molecular C—H(...)O inter­actions.

Related literature

For biological activity, see: Nieto et al. (2005 [triangle]); Yang et al. (2002 [triangle]). For the structures of closely related compounds, see: Chakkaravarthi et al. (2007 [triangle], 2008 [triangle]).

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Object name is e-64-0o732-scheme1.jpg

Experimental

Crystal data

  • C19H18BrNO5S
  • M r = 452.31
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o732-efi1.jpg
  • a = 8.9988 (3) Å
  • b = 9.2343 (2) Å
  • c = 11.6068 (3) Å
  • α = 82.524 (1)°
  • β = 87.666 (2)°
  • γ = 84.942 (3)°
  • V = 952.16 (5) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 2.30 mm−1
  • T = 295 (2) K
  • 0.20 × 0.20 × 0.16 mm

Data collection

  • Bruker Kappa APEXII diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.593, T max = 0.692
  • 25160 measured reflections
  • 6169 independent reflections
  • 4163 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.044
  • wR(F 2) = 0.127
  • S = 1.03
  • 6169 reflections
  • 254 parameters
  • 3 restraints
  • H-atom parameters constrained
  • Δρmax = 0.68 e Å−3
  • Δρmin = −0.89 e Å−3

Data collection: APEX2 (Bruker, 2004 [triangle]); cell refinement: APEX2; data reduction: APEX2; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: PLATON (Spek, 2003 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007319/rk2082sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007319/rk2082Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors acknowledge the Sophisticated Analytical Instrument Facility, Indian Institute of Technology, Madras, for the data collection.

supplementary crystallographic information

Comment

In continuation of our studies of benzenesulfonamide derivatives, which are known to exhibit anti–bacterial (Nieto et al., 2005) anti–tumour (Yang et al., 2002) activities, we report the crystal structure of the title compound (I). The geometric parameters of the molecule of I (Fig. 1) agree well with the reported structures (Chakkaravarthi et al., 2007; Chakkaravarthi et al., 2008).

The plane of the phenyl ring forms a dihedral angle of 76.99 (6)° with the indole ring system. The N1—S1—C1 plane is orthogonal to indole ring (dihedral angle 88.70 (7)°) and makes 75.97 (9)° with the phenyl ring. The plane of indole ring is almost coplanar (dihedral angle 2.66 (7)°) with the ester group and makes 6.33 (18)° with the methoxy group.

The torsion angles O2–S1–N1–C7 and O1–S1–N1–C14 [-30.0 (2)° and 27.3 (2)°, respectively] indicate syn–conformation of the sulfonyl moiety. The Br1 atom is disordered over two positions with the site occupancy factors of 0.833 (14) and 0.167 (14). The molecular packing is stabilized by weak intramolecular C—H···O interactions and the crystal packing of I (Fig. 2) is stabilized by weak intermolecular C—H···O interactions (see Table).

Experimental

Ethyl 2-(methyl)-5-methoxy-1-(phenylsulfonyl)-1H-indole-3-carboxylate (1g, 2.2 mmol), N–bromo succinimide (0.4 g, 2.3 mmol), azo–bis–isobutyronitrile (50 mg) were dissolved in 50 ml of carbon tetrachloride. Refluxed on a waterbath for 2hr. Cooled to room temperature. Succinimide was filtered off over sodium sulfate. Filtrate was evaporated under reduced pressure. Product was recrystallized from methanol. Yield: 78%.

Refinement

The H atoms were positioned geometrically and refined using riding model with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(C) for aromatic C—H, C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for CH2 and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for CH3. The site occupancy factors for disordered Br atom is refined as Br1= 0.833 (14) and Br1A = 0.167 (14) during anisotropic refinement. The C15—Br1A distance was restrained to 1.91 (10) Å. The anisotropic displacement parameters of Br1 and Br1A were set equal by the command EADP and the anisotropic thermal parameters of C4, C5, C15 and Br1A atoms were restrained with DELU in the final cycles of refinement (Sheldrick, 2008).

Figures

Fig. 1.
The molecular structure of I, with atom labeling scheme. Displacement ellipsoids are drawn at 50% probability level. H atoms are presented as a small spheres of arbitrary radius. Only major fragment for disordered Br1 and C15 are drawn. Intramolecular ...
Fig. 2.
The packing of I, viewed down the a axis. Intermolecular H–bonds are shown as dashed lines H atoms not involving hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) -x+1, -y+1, -z+2; (ii) x, y+1, z].

Crystal data

C19H18BrNO5SZ = 2
Mr = 452.31F000 = 460
Triclinic, P1Dx = 1.578 Mg m3
Hall symbol: -P 1Mo Kα radiation λ = 0.71073 Å
a = 8.9988 (3) ÅCell parameters from 8207 reflections
b = 9.2343 (2) Åθ = 2.2–27.5º
c = 11.6068 (3) ŵ = 2.30 mm1
α = 82.524 (1)ºT = 295 (2) K
β = 87.666 (2)ºBlock, colourless
γ = 84.942 (3)º0.20 × 0.20 × 0.16 mm
V = 952.16 (5) Å3

Data collection

Bruker Kappa APEXII diffractometer6169 independent reflections
Radiation source: Fine–focus sealed tube4163 reflections with I > 2σ(I)
Monochromator: GraphiteRint = 0.027
T = 295(2) Kθmax = 31.2º
ω and [var phi] scansθmin = 1.8º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996)h = −13→13
Tmin = 0.593, Tmax = 0.692k = −13→13
25160 measured reflectionsl = −16→16

Refinement

Refinement on F2Secondary atom site location: Difmap
Least-squares matrix: FullHydrogen site location: Geom
R[F2 > 2σ(F2)] = 0.044H-atom parameters constrained
wR(F2) = 0.127  w = 1/[σ2(Fo2) + (0.054P)2 + 0.4811P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
6169 reflectionsΔρmax = 0.68 e Å3
254 parametersΔρmin = −0.89 e Å3
3 restraintsExtinction correction: None
Primary atom site location: Direct

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

xyzUiso*/UeqOcc. (<1)
Br10.2859 (3)−0.0105 (2)0.5880 (3)0.0695 (4)0.833 (14)
Br1A0.2613 (8)0.0063 (7)0.6105 (7)0.0695 (4)0.167 (14)
S10.53695 (6)0.26331 (6)0.73409 (5)0.04656 (14)
O10.6066 (2)0.3534 (2)0.80232 (18)0.0623 (5)
O20.6249 (2)0.1714 (2)0.66452 (19)0.0688 (6)
O30.1927 (3)0.2237 (2)1.26357 (17)0.0714 (6)
O40.1493 (2)−0.18350 (18)1.02343 (16)0.0551 (4)
O50.2440 (3)−0.2589 (2)0.8592 (2)0.0783 (6)
N10.4384 (2)0.15286 (19)0.82973 (15)0.0410 (4)
C10.4041 (2)0.3722 (2)0.64784 (18)0.0407 (4)
C20.3253 (3)0.4881 (3)0.6931 (2)0.0499 (5)
H20.34050.50620.76860.060*
C30.2243 (3)0.5759 (3)0.6245 (3)0.0627 (7)
H30.17030.65450.65370.075*
C40.2020 (4)0.5490 (3)0.5135 (3)0.0690 (7)
H40.13210.60850.46820.083*
C50.2818 (4)0.4352 (3)0.4690 (2)0.0693 (7)
H50.26630.41780.39350.083*
C60.3860 (3)0.3453 (3)0.5360 (2)0.0561 (6)
H60.44220.26880.50580.067*
C70.3878 (2)0.0171 (2)0.81460 (18)0.0412 (4)
C80.3026 (2)−0.0297 (2)0.90984 (18)0.0393 (4)
C90.2973 (2)0.0781 (2)0.98934 (17)0.0380 (4)
C100.2300 (3)0.0839 (3)1.10015 (19)0.0452 (5)
H100.17420.00931.13530.054*
C110.2498 (3)0.2044 (3)1.1549 (2)0.0510 (5)
C120.3333 (3)0.3160 (3)1.1024 (2)0.0555 (6)
H120.34440.39581.14170.067*
C130.3993 (3)0.3117 (3)0.9951 (2)0.0516 (5)
H130.45470.38710.96070.062*
C140.3808 (2)0.1902 (2)0.93842 (18)0.0399 (4)
C150.4242 (3)−0.0591 (3)0.7108 (2)0.0560 (5)
H15A0.4287−0.16400.73460.067*0.833 (14)
H15B0.5226−0.03560.68080.067*0.833 (14)
H15C0.4302−0.16460.73120.067*0.167 (14)
H15D0.5176−0.03060.67360.067*0.167 (14)
C160.0958 (4)0.1221 (4)1.3175 (3)0.0719 (8)
H16A0.01090.12211.27000.108*
H16B0.06300.14871.39220.108*
H16C0.14740.02591.32710.108*
C170.2311 (3)−0.1686 (2)0.9262 (2)0.0470 (5)
C180.0781 (3)−0.3188 (3)1.0520 (3)0.0738 (9)
H18A0.1507−0.40231.04880.089*
H18B0.0008−0.32430.99720.089*
C190.0120 (4)−0.3191 (5)1.1716 (4)0.1037 (15)
H19A0.0896−0.31501.22520.156*
H19B−0.0375−0.40701.19300.156*
H19C−0.0589−0.23541.17390.156*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0960 (5)0.0791 (4)0.0381 (5)−0.0300 (4)−0.0142 (5)−0.0064 (4)
Br1A0.0960 (5)0.0791 (4)0.0381 (5)−0.0300 (4)−0.0142 (5)−0.0064 (4)
S10.0417 (3)0.0457 (3)0.0503 (3)−0.0032 (2)0.0003 (2)0.0003 (2)
O10.0509 (10)0.0655 (11)0.0719 (12)−0.0198 (8)−0.0153 (8)0.0002 (9)
O20.0616 (11)0.0617 (11)0.0763 (13)0.0099 (9)0.0226 (10)−0.0013 (10)
O30.0890 (15)0.0806 (14)0.0485 (10)−0.0023 (11)0.0037 (10)−0.0285 (10)
O40.0634 (10)0.0476 (9)0.0544 (10)−0.0169 (8)−0.0054 (8)0.0019 (7)
O50.1144 (18)0.0565 (11)0.0729 (13)−0.0309 (11)0.0018 (12)−0.0271 (10)
N10.0493 (10)0.0366 (8)0.0368 (9)−0.0027 (7)−0.0047 (7)−0.0028 (7)
C10.0475 (11)0.0364 (10)0.0378 (10)−0.0087 (8)−0.0007 (8)0.0004 (8)
C20.0592 (14)0.0448 (12)0.0446 (12)−0.0003 (10)−0.0010 (10)−0.0046 (9)
C30.0667 (17)0.0526 (14)0.0643 (17)0.0067 (12)−0.0043 (13)0.0026 (12)
C40.0731 (18)0.0632 (15)0.0666 (17)−0.0116 (12)−0.0220 (14)0.0176 (12)
C50.100 (2)0.0681 (16)0.0423 (13)−0.0282 (13)−0.0172 (13)0.0013 (11)
C60.0832 (18)0.0457 (12)0.0405 (12)−0.0136 (12)0.0018 (12)−0.0054 (9)
C70.0482 (11)0.0377 (10)0.0378 (10)0.0006 (8)−0.0085 (9)−0.0055 (8)
C80.0470 (11)0.0349 (9)0.0367 (10)−0.0014 (8)−0.0108 (8)−0.0048 (7)
C90.0435 (10)0.0352 (9)0.0349 (9)0.0020 (8)−0.0096 (8)−0.0046 (7)
C100.0501 (12)0.0476 (12)0.0379 (10)−0.0016 (9)−0.0074 (9)−0.0051 (9)
C110.0588 (14)0.0557 (13)0.0393 (11)0.0059 (11)−0.0081 (10)−0.0143 (10)
C120.0738 (17)0.0448 (12)0.0515 (13)−0.0005 (11)−0.0141 (12)−0.0183 (10)
C130.0666 (15)0.0386 (11)0.0517 (13)−0.0078 (10)−0.0130 (11)−0.0074 (9)
C140.0467 (11)0.0357 (10)0.0373 (10)0.0005 (8)−0.0099 (8)−0.0045 (8)
C150.0730 (15)0.0533 (14)0.0440 (12)−0.0058 (11)0.0002 (9)−0.0152 (10)
C160.0666 (18)0.097 (2)0.0486 (15)0.0153 (16)0.0053 (13)−0.0143 (15)
C170.0561 (13)0.0395 (11)0.0464 (12)−0.0060 (9)−0.0160 (10)−0.0033 (9)
C180.0631 (16)0.0593 (16)0.096 (2)−0.0238 (13)−0.0233 (16)0.0205 (15)
C190.065 (2)0.128 (3)0.105 (3)−0.030 (2)−0.0010 (19)0.048 (3)

Geometric parameters (Å, °)

Br1—C151.914 (3)C7—C151.484 (3)
Br1A—C151.9152 (10)C8—C91.439 (3)
S1—O21.417 (2)C8—C171.472 (3)
S1—O11.419 (2)C9—C141.389 (3)
S1—N11.6862 (19)C9—C101.405 (3)
S1—C11.751 (2)C10—C111.379 (3)
O3—C111.370 (3)C10—H100.9300
O3—C161.407 (4)C11—C121.390 (4)
O4—C171.320 (3)C12—C131.362 (4)
O4—C181.448 (3)C12—H120.9300
O5—C171.208 (3)C13—C141.398 (3)
N1—C71.405 (3)C13—H130.9300
N1—C141.417 (3)C15—H15A0.9700
C1—C61.372 (3)C15—H15B0.9700
C1—C21.381 (3)C15—H15C0.9700
C2—C31.371 (4)C15—H15D0.9700
C2—H20.9300C16—H16A0.9600
C3—C41.369 (4)C16—H16B0.9600
C3—H30.9300C16—H16C0.9600
C4—C51.365 (5)C18—C191.487 (5)
C4—H40.9300C18—H18A0.9700
C5—C61.388 (4)C18—H18B0.9700
C5—H50.9300C19—H19A0.9600
C6—H60.9300C19—H19B0.9600
C7—C81.364 (3)C19—H19C0.9600
O2—S1—O1120.09 (13)C11—C12—H12119.1
O2—S1—N1106.72 (11)C12—C13—C14117.7 (2)
O1—S1—N1105.29 (11)C12—C13—H13121.1
O2—S1—C1109.30 (12)C14—C13—H13121.1
O1—S1—C1108.93 (11)C9—C14—C13121.2 (2)
N1—S1—C1105.49 (10)C9—C14—N1107.98 (17)
C11—O3—C16117.9 (2)C13—C14—N1130.8 (2)
C17—O4—C18117.3 (2)C7—C15—Br1114.7 (2)
C7—N1—C14107.77 (17)C7—C15—Br1A103.7 (4)
C7—N1—S1127.88 (15)C7—C15—H15A108.6
C14—N1—S1124.15 (15)Br1—C15—H15A108.6
C6—C1—C2121.7 (2)Br1A—C15—H15A111.8
C6—C1—S1119.67 (19)C7—C15—H15B108.6
C2—C1—S1118.53 (18)Br1—C15—H15B108.6
C3—C2—C1118.6 (2)Br1A—C15—H15B116.3
C3—C2—H2120.7H15A—C15—H15B107.6
C1—C2—H2120.7C7—C15—H15C111.1
C4—C3—C2120.6 (3)Br1—C15—H15C107.3
C4—C3—H3119.7Br1A—C15—H15C111.0
C2—C3—H3119.7H15B—C15—H15C106.2
C5—C4—C3120.4 (3)C7—C15—H15D111.1
C5—C4—H4119.8Br1—C15—H15D102.7
C3—C4—H4119.8Br1A—C15—H15D110.4
C4—C5—C6120.3 (3)H15A—C15—H15D111.1
C4—C5—H5119.8H15C—C15—H15D109.5
C6—C5—H5119.8O3—C16—H16A109.5
C1—C6—C5118.4 (3)O3—C16—H16B109.5
C1—C6—H6120.8H16A—C16—H16B109.5
C5—C6—H6120.8O3—C16—H16C109.5
C8—C7—N1108.66 (18)H16A—C16—H16C109.5
C8—C7—C15127.3 (2)H16B—C16—H16C109.5
N1—C7—C15124.1 (2)O5—C17—O4123.3 (2)
C7—C8—C9108.47 (18)O5—C17—C8124.7 (2)
C7—C8—C17124.5 (2)O4—C17—C8112.02 (19)
C9—C8—C17127.0 (2)O4—C18—C19107.3 (3)
C14—C9—C10120.41 (19)O4—C18—H18A110.3
C14—C9—C8107.12 (18)C19—C18—H18A110.3
C10—C9—C8132.5 (2)O4—C18—H18B110.3
C11—C10—C9117.5 (2)C19—C18—H18B110.3
C11—C10—H10121.2H18A—C18—H18B108.5
C9—C10—H10121.2C18—C19—H19A109.5
O3—C11—C10123.9 (2)C18—C19—H19B109.5
O3—C11—C12114.8 (2)H19A—C19—H19B109.5
C10—C11—C12121.3 (2)C18—C19—H19C109.5
C13—C12—C11121.8 (2)H19A—C19—H19C109.5
C13—C12—H12119.1H19B—C19—H19C109.5
O2—S1—N1—C7−30.0 (2)C17—C8—C9—C101.3 (4)
O1—S1—N1—C7−158.62 (19)C14—C9—C10—C110.3 (3)
C1—S1—N1—C786.2 (2)C8—C9—C10—C11178.5 (2)
O2—S1—N1—C14155.94 (18)C16—O3—C11—C10−6.6 (4)
O1—S1—N1—C1427.3 (2)C16—O3—C11—C12174.3 (2)
C1—S1—N1—C14−87.87 (18)C9—C10—C11—O3−179.0 (2)
O2—S1—C1—C68.6 (2)C9—C10—C11—C120.0 (3)
O1—S1—C1—C6141.6 (2)O3—C11—C12—C13179.0 (2)
N1—S1—C1—C6−105.8 (2)C10—C11—C12—C13−0.1 (4)
O2—S1—C1—C2−168.24 (19)C11—C12—C13—C14−0.1 (4)
O1—S1—C1—C2−35.3 (2)C10—C9—C14—C13−0.5 (3)
N1—S1—C1—C277.3 (2)C8—C9—C14—C13−179.1 (2)
C6—C1—C2—C31.4 (4)C10—C9—C14—N1178.12 (19)
S1—C1—C2—C3178.2 (2)C8—C9—C14—N1−0.5 (2)
C1—C2—C3—C40.1 (4)C12—C13—C14—C90.4 (3)
C2—C3—C4—C5−0.9 (5)C12—C13—C14—N1−177.8 (2)
C3—C4—C5—C60.2 (5)C7—N1—C14—C90.6 (2)
C2—C1—C6—C5−2.1 (4)S1—N1—C14—C9175.69 (14)
S1—C1—C6—C5−178.8 (2)C7—N1—C14—C13179.0 (2)
C4—C5—C6—C11.2 (4)S1—N1—C14—C13−5.9 (3)
C14—N1—C7—C8−0.4 (2)C8—C7—C15—Br190.2 (3)
S1—N1—C7—C8−175.24 (15)N1—C7—C15—Br1−90.1 (2)
C14—N1—C7—C15179.9 (2)C8—C7—C15—Br1A87.5 (3)
S1—N1—C7—C155.0 (3)N1—C7—C15—Br1A−92.8 (3)
N1—C7—C8—C90.0 (2)C18—O4—C17—O52.9 (4)
C15—C7—C8—C9179.8 (2)C18—O4—C17—C8−177.4 (2)
N1—C7—C8—C17−179.39 (19)C7—C8—C17—O52.7 (4)
C15—C7—C8—C170.4 (4)C9—C8—C17—O5−176.6 (2)
C7—C8—C9—C140.3 (2)C7—C8—C17—O4−176.9 (2)
C17—C8—C9—C14179.7 (2)C9—C8—C17—O43.8 (3)
C7—C8—C9—C10−178.1 (2)C17—O4—C18—C19171.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C12—H12···O1i0.932.563.472 (3)165
C2—H2···O5ii0.932.603.235 (3)126
C6—H6···O20.932.542.908 (4)104
C10—H10···O40.932.372.892 (3)116
C13—H13···O10.932.282.863 (3)120
C15—H15A···O50.972.312.911 (4)119
C15—H15D···O20.972.162.895 (4)131

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RK2082).

References

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