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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2008 Mar 29;64(Pt 4):o749. doi: 10.1107/S1600536808007678

3-Bromo­meth­yl-2-chloro­meth­yl-1-phenyl­sulfon­yl-1H-indole

G Chakkaravarthi a,*, V Dhayalan b, A K Mohanakrishnan b, V Manivannan c
PMCID: PMC2960947  PMID: 21202139

Abstract

In the title compound, C16H13BrClNO2S, the indole mean plane forms a dihedral angle of 73.59 (19)° with the phenyl ring. The mol­ecular structure is stabilized by weak intra­molecular C—H⋯O inter­actions. The Br atom is disordered over two positions with site occupancy factors of 0.7 and 0.3.

Related literature

For related crystal structures, see: Chakkaravarthi et al. (2007 ▶, 2008 ▶). For the biological activities of indole derivatives, see: Chai et al. (2006 ▶); Nieto et al. (2005 ▶); Olgen & Coban (2003 ▶).graphic file with name e-64-0o749-scheme1.jpg

Experimental

Crystal data

  • C16H13BrClNO2S

  • M r = 398.69

  • Monoclinic, Inline graphic

  • a = 11.8501 (9) Å

  • b = 16.3525 (13) Å

  • c = 8.5793 (6) Å

  • β = 108.766 (3)°

  • V = 1574.1 (2) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 2.92 mm−1

  • T = 295 (2) K

  • 0.16 × 0.14 × 0.14 mm

Data collection

  • Bruker Kappa APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.559, T max = 0.665

  • 14367 measured reflections

  • 2770 independent reflections

  • 1822 reflections with I > 2σ(I)

  • R int = 0.045

Refinement

  • R[F 2 > 2σ(F 2)] = 0.066

  • wR(F 2) = 0.231

  • S = 1.06

  • 2770 reflections

  • 209 parameters

  • 12 restraints

  • H-atom parameters constrained

  • Δρmax = 0.42 e Å−3

  • Δρmin = −0.92 e Å−3

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

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007678/bt2689sup1.cif

e-64-0o749-sup1.cif (18.4KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007678/bt2689Isup2.hkl

e-64-0o749-Isup2.hkl (133.2KB, hkl)

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A D—H H⋯A D⋯A D—H⋯A
C6—H6⋯O2 0.93 2.51 2.877 (9) 104
C13—H13⋯O1 0.93 2.31 2.873 (10) 118
C15—H15B⋯O2 0.97 2.17 2.939 (10) 136
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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 indole derivatives, which are known to exhibit anti-oxidant activity (Olgen & Coban, 2003), antihepatitis B virus activities (Chai et al., 2006) and antibacterial (Nieto et al., 2005) 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, 2008). The indole mean plane forms a dihedral angle of 73.59 (19)° with the phenyl ring. The N1—S1—C1 plane is almost orthogonal to indole ring (dihedral angle 82.30 (22)°) and makes 76.93 (22)° with the phenyl ring. The indole mean plane and C8—C16—BR1 plane are nearly orthogonal to each other forming a dihedral angle of 82.23 (0.29)°.

The sum of bond angles around N1 (359.99°) shows that N1 is sp2-hybridized. The torsion angles O1—S1—N1—C14 and O2—S1—N1—C7 [17.8 (6)° and -33.4 (6)°, respectively] indicate the syn conformation of the sulfonyl moiety. The molecular structure is stabilized by weak intramolecular C—H···O interactions.

Experimental

1-(Phenylsulfonyl)-3-(bromomethyl)-2-methylindole (0.5 g, 1.37 mmol) was dissolved in dry ccl4(10 ml) and then powdered N-chloro succinimide was added. To this, azobisisobutyronitrle (50 mg) was also added and then refluxed for 2 h on a waterbath. After the reaction was completed, succinimide was floated on the surface of the reaction mixture. It was then filtered off and washed with CCl4 (3 ml). The solvent was removed carefully under vacuo. The crude product was recrystallized from CCl4. Yield:76 percentage.

Refinement

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 and C—H = 0.97 Å and Uiso(H) = 1.2Ueq(C) for CH2. The Br atom is disordered over two positions with the occupancies of 0.709 (16) and 0.291 (16), respectively. The distances C1—C2, C2—C3, C3—C4, C4—C5, C10—C11 and C11—C12 were restrained to 1.395 (1) Å, the distances C16—BR1 and C16—Br1A were restrained to 1.91 (10) Å and the distance CL1—C15 was restrained to 1.76 (5) Å. The anisotropic thermal parameters of C15, C16, BR1, BR1A, CL1 atoms were restrained with DELU in the final cycles of the refinement (Sheldrick, 2008).

Figures

Fig. 1.

Fig. 1.

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The molecular structure of (I) showing the atomic labels and 50% probability displacement ellipsoids for non-H atoms. Only major parts of the disordered atoms are drawn. Intramolecular H-bonds are shown as dashed lines.

Crystal data

C16H13BrClNO2S F000 = 800
Mr = 398.69 Dx = 1.682 Mg m−3
Monoclinic, P21/c Mo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ybc Cell parameters from 4037 reflections
a = 11.8501 (9) Å θ = 2.5–25.0º
b = 16.3525 (13) Å µ = 2.92 mm−1
c = 8.5793 (6) Å T = 295 (2) K
β = 108.766 (3)º Block, colourless
V = 1574.1 (2) Å3 0.16 × 0.14 × 0.14 mm
Z = 4
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Data collection

Bruker Kappa APEXII diffractometer 2770 independent reflections
Radiation source: fine-focus sealed tube 1822 reflections with I > 2σ(I)
Monochromator: graphite Rint = 0.045
T = 295(2) K θmax = 25.0º
ω and φ scans θmin = 2.2º
Absorption correction: multi-scan(SADABS; Sheldrick, 1996) h = −14→13
Tmin = 0.559, Tmax = 0.665 k = −19→19
14367 measured reflections l = −10→10
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Refinement

Refinement on F2 Secondary atom site location: difference Fourier map
Least-squares matrix: full Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066 H-atom parameters constrained
wR(F2) = 0.231   w = 1/[σ2(Fo2) + (0.127P)2 + 1.9456P] where P = (Fo2 + 2Fc2)/3
S = 1.06 (Δ/σ)max < 0.001
2770 reflections Δρmax = 0.42 e Å−3
209 parameters Δρmin = −0.91 e Å−3
12 restraints Extinction correction: none
Primary atom site location: structure-invariant direct methods
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq Occ. (<1)
Cl1 0.90925 (16) −0.10531 (12) 0.5085 (3) 0.0872 (6)
Br1 0.8135 (6) 0.1043 (5) 0.3205 (5) 0.1572 (16) 0.709 (16)
Br1A 0.7901 (4) 0.1251 (3) 0.3139 (9) 0.093 (2) 0.291 (16)
S1 0.70049 (14) −0.13649 (11) 0.8192 (2) 0.0743 (6)
O1 0.6340 (5) −0.1191 (4) 0.9258 (8) 0.114 (2)
O2 0.6743 (5) −0.2077 (3) 0.7212 (8) 0.109 (2)
N1 0.6795 (4) −0.0573 (3) 0.6922 (5) 0.0539 (11)
C1 0.8512 (6) −0.1369 (4) 0.9320 (7) 0.0655 (17)
C2 0.8952 (7) −0.0826 (5) 1.0604 (8) 0.097 (2)
H2 0.8449 −0.0449 1.0854 0.117*
C3 1.0161 (8) −0.0849 (8) 1.1523 (11) 0.127 (4)
H3 1.0474 −0.0485 1.2387 0.153*
C4 1.0885 (9) −0.1418 (7) 1.1133 (13) 0.122 (4)
H4 1.1688 −0.1441 1.1753 0.147*
C5 1.0442 (8) −0.1951 (6) 0.9845 (13) 0.113 (3)
H5 1.0947 −0.2325 0.9590 0.135*
C6 0.9256 (7) −0.1932 (5) 0.8934 (10) 0.086 (2)
H6 0.8953 −0.2295 0.8065 0.103*
C7 0.7000 (5) −0.0556 (3) 0.5384 (7) 0.0574 (14)
C8 0.6681 (5) 0.0197 (3) 0.4715 (6) 0.0535 (14)
C9 0.6288 (5) 0.0680 (3) 0.5809 (5) 0.0463 (12)
C10 0.5887 (6) 0.1477 (4) 0.5707 (7) 0.0622 (15)
H10 0.5837 0.1796 0.4790 0.075*
C11 0.5563 (6) 0.1790 (4) 0.6984 (8) 0.078 (2)
H11 0.5295 0.2327 0.6939 0.094*
C12 0.5633 (7) 0.1313 (5) 0.8332 (9) 0.083 (2)
H12 0.5406 0.1537 0.9182 0.099*
C13 0.6026 (6) 0.0519 (5) 0.8471 (6) 0.0687 (18)
H13 0.6064 0.0203 0.9388 0.082*
C14 0.6365 (4) 0.0206 (3) 0.7184 (6) 0.0468 (12)
C15 0.7557 (4) −0.1232 (4) 0.4743 (11) 0.086 (2)
H15A 0.7151 −0.1294 0.3572 0.103*
H15B 0.7464 −0.1739 0.5278 0.103*
C16 0.6722 (5) 0.0443 (4) 0.3064 (7) 0.084 (2)
H16A 0.6030 0.0777 0.2520 0.101* 0.709 (16)
H16B 0.6686 −0.0042 0.2400 0.101* 0.709 (16)
H16C 0.6052 0.0802 0.2560 0.101* 0.291 (16)
H16D 0.6645 −0.0033 0.2363 0.101* 0.291 (16)
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
Cl1 0.0663 (11) 0.0872 (13) 0.1176 (15) 0.0181 (9) 0.0429 (10) −0.0109 (10)
Br1 0.235 (3) 0.159 (3) 0.106 (2) −0.112 (2) 0.095 (2) −0.0245 (15)
Br1A 0.063 (4) 0.105 (3) 0.098 (3) −0.014 (2) 0.008 (2) 0.041 (3)
S1 0.0540 (9) 0.0688 (11) 0.0926 (12) −0.0071 (8) 0.0129 (8) 0.0402 (9)
O1 0.082 (3) 0.142 (5) 0.130 (5) 0.015 (3) 0.053 (3) 0.087 (4)
O2 0.087 (3) 0.059 (3) 0.144 (5) −0.029 (3) −0.016 (3) 0.035 (3)
N1 0.057 (3) 0.049 (3) 0.052 (2) 0.000 (2) 0.012 (2) 0.013 (2)
C1 0.061 (4) 0.067 (4) 0.065 (4) −0.010 (3) 0.015 (3) 0.028 (3)
C2 0.100 (6) 0.123 (7) 0.058 (4) −0.002 (5) 0.010 (4) 0.011 (4)
C3 0.123 (8) 0.145 (10) 0.079 (6) −0.039 (8) −0.016 (6) 0.010 (6)
C4 0.077 (6) 0.138 (9) 0.121 (8) −0.020 (6) −0.010 (6) 0.051 (7)
C5 0.076 (6) 0.116 (7) 0.139 (8) 0.024 (5) 0.025 (6) 0.041 (7)
C6 0.072 (5) 0.077 (5) 0.096 (5) 0.011 (4) 0.009 (4) 0.019 (4)
C7 0.064 (4) 0.051 (3) 0.059 (3) −0.005 (3) 0.023 (3) −0.008 (3)
C8 0.070 (4) 0.053 (3) 0.039 (3) −0.007 (3) 0.020 (2) −0.002 (2)
C9 0.047 (3) 0.052 (3) 0.034 (2) −0.002 (2) 0.005 (2) −0.001 (2)
C10 0.066 (4) 0.050 (3) 0.061 (3) 0.006 (3) 0.007 (3) 0.005 (3)
C11 0.066 (4) 0.066 (4) 0.095 (5) 0.014 (3) 0.014 (4) −0.021 (4)
C12 0.071 (4) 0.106 (6) 0.073 (4) 0.003 (4) 0.028 (4) −0.036 (4)
C13 0.062 (4) 0.104 (5) 0.037 (3) −0.001 (4) 0.013 (3) −0.002 (3)
C14 0.043 (3) 0.057 (3) 0.038 (2) −0.003 (2) 0.009 (2) 0.004 (2)
C15 0.079 (3) 0.074 (5) 0.110 (6) −0.007 (4) 0.039 (4) −0.026 (4)
C16 0.134 (5) 0.073 (4) 0.051 (3) −0.026 (4) 0.038 (4) 0.001 (3)
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Geometric parameters (Å, °)

Cl1—C15 1.772 (4) C7—C8 1.359 (8)
Br1—C16 1.9114 (11) C7—C15 1.481 (9)
Br1A—C16 1.9084 (11) C8—C9 1.415 (8)
S1—O2 1.411 (6) C8—C16 1.489 (7)
S1—O1 1.415 (6) C9—C10 1.381 (8)
S1—N1 1.659 (4) C9—C14 1.390 (7)
S1—C1 1.737 (6) C10—C11 1.371 (7)
N1—C14 1.417 (7) C10—H10 0.9300
N1—C7 1.417 (7) C11—C12 1.375 (8)
C1—C2 1.380 (8) C11—H11 0.9300
C1—C6 1.386 (10) C12—C13 1.372 (10)
C2—C3 1.396 (8) C12—H12 0.9300
C2—H2 0.9300 C13—C14 1.387 (8)
C3—C4 1.379 (9) C13—H13 0.9300
C3—H3 0.9300 C15—H15A 0.9700
C4—C5 1.371 (9) C15—H15B 0.9700
C4—H4 0.9300 C16—H16A 0.9700
C5—C6 1.371 (12) C16—H16B 0.9700
C5—H5 0.9300 C16—H16C 0.9700
C6—H6 0.9300 C16—H16D 0.9700
O2—S1—O1 119.3 (4) C9—C10—H10 120.6
O2—S1—N1 107.2 (3) C10—C11—C12 120.3 (6)
O1—S1—N1 105.7 (3) C10—C11—H11 119.9
O2—S1—C1 108.5 (3) C12—C11—H11 119.9
O1—S1—C1 109.1 (4) C13—C12—C11 122.5 (6)
N1—S1—C1 106.2 (3) C13—C12—H12 118.8
C14—N1—C7 108.0 (4) C11—C12—H12 118.8
C14—N1—S1 125.7 (4) C12—C13—C14 117.1 (6)
C7—N1—S1 126.3 (4) C12—C13—H13 121.4
C2—C1—C6 120.8 (7) C14—C13—H13 121.4
C2—C1—S1 119.9 (6) C13—C14—C9 120.9 (5)
C6—C1—S1 119.3 (5) C13—C14—N1 131.9 (5)
C1—C2—C3 119.3 (8) C9—C14—N1 107.2 (4)
C1—C2—H2 120.4 C7—C15—Cl1 111.8 (4)
C3—C2—H2 120.4 C7—C15—H15A 109.3
C4—C3—C2 119.1 (9) Cl1—C15—H15A 109.3
C4—C3—H3 120.4 C7—C15—H15B 109.3
C2—C3—H3 120.4 Cl1—C15—H15B 109.3
C5—C4—C3 121.2 (9) H15A—C15—H15B 107.9
C5—C4—H4 119.4 C8—C16—Br1A 113.8 (4)
C3—C4—H4 119.4 C8—C16—Br1 112.0 (4)
C6—C5—C4 120.1 (9) C8—C16—H16A 109.2
C6—C5—H5 119.9 Br1A—C16—H16A 97.1
C4—C5—H5 119.9 Br1—C16—H16A 109.2
C5—C6—C1 119.5 (8) C8—C16—H16B 109.2
C5—C6—H6 120.3 Br1A—C16—H16B 118.6
C1—C6—H6 120.3 Br1—C16—H16B 109.2
C8—C7—N1 107.6 (5) H16A—C16—H16B 107.9
C8—C7—C15 128.1 (6) C8—C16—H16C 108.4
N1—C7—C15 124.2 (6) Br1A—C16—H16C 94.7
C7—C8—C9 109.4 (5) Br1—C16—H16C 107.0
C7—C8—C16 123.8 (6) H16B—C16—H16C 111.0
C9—C8—C16 126.7 (5) C8—C16—H16D 110.3
C10—C9—C14 120.5 (5) Br1A—C16—H16D 119.9
C10—C9—C8 131.7 (5) Br1—C16—H16D 110.9
C14—C9—C8 107.8 (5) H16A—C16—H16D 104.9
C11—C10—C9 118.7 (5) H16C—C16—H16D 108.0
C11—C10—H10 120.6
O2—S1—N1—C14 146.0 (5) C15—C7—C8—C16 7.1 (9)
O1—S1—N1—C14 17.8 (6) C7—C8—C9—C10 179.3 (6)
C1—S1—N1—C14 −98.1 (5) C16—C8—C9—C10 −2.1 (10)
O2—S1—N1—C7 −33.4 (6) C7—C8—C9—C14 −0.3 (6)
O1—S1—N1—C7 −161.6 (5) C16—C8—C9—C14 178.3 (5)
C1—S1—N1—C7 82.5 (5) C14—C9—C10—C11 −0.2 (8)
O2—S1—C1—C2 −167.5 (6) C8—C9—C10—C11 −179.8 (6)
O1—S1—C1—C2 −36.0 (6) C9—C10—C11—C12 −0.4 (10)
N1—S1—C1—C2 77.6 (6) C10—C11—C12—C13 0.3 (11)
O2—S1—C1—C6 11.3 (6) C11—C12—C13—C14 0.4 (10)
O1—S1—C1—C6 142.8 (5) C12—C13—C14—C9 −0.9 (8)
N1—S1—C1—C6 −103.7 (5) C12—C13—C14—N1 −179.4 (6)
C6—C1—C2—C3 −0.2 (11) C10—C9—C14—C13 0.9 (8)
S1—C1—C2—C3 178.6 (7) C8—C9—C14—C13 −179.4 (5)
C1—C2—C3—C4 −0.5 (15) C10—C9—C14—N1 179.7 (5)
C2—C3—C4—C5 1.1 (17) C8—C9—C14—N1 −0.6 (6)
C3—C4—C5—C6 −1.0 (16) C7—N1—C14—C13 179.9 (6)
C4—C5—C6—C1 0.3 (13) S1—N1—C14—C13 0.4 (8)
C2—C1—C6—C5 0.2 (11) C7—N1—C14—C9 1.3 (6)
S1—C1—C6—C5 −178.5 (6) S1—N1—C14—C9 −178.2 (4)
C14—N1—C7—C8 −1.5 (6) C8—C7—C15—Cl1 76.0 (8)
S1—N1—C7—C8 178.0 (4) N1—C7—C15—Cl1 −98.7 (7)
C14—N1—C7—C15 174.1 (5) C7—C8—C16—Br1A −112.1 (6)
S1—N1—C7—C15 −6.4 (8) C9—C8—C16—Br1A 69.5 (8)
N1—C7—C8—C9 1.1 (6) C7—C8—C16—Br1 −98.2 (7)
C15—C7—C8—C9 −174.3 (5) C9—C8—C16—Br1 83.4 (8)
N1—C7—C8—C16 −177.5 (5)
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Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A
C6—H6···O2 0.93 2.51 2.877 (9) 104
C13—H13···O1 0.93 2.31 2.873 (10) 118
C15—H15B···O2 0.97 2.17 2.939 (10) 136
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BT2689).

References

  1. Bruker (2004). APEX2 Bruker AXS Inc., Madison, Wisconsin, USA.
  2. Chai, H., Zhao, C. & Gong, P. (2006). Bioorg. Med. Chem.14, 911–917. [DOI] [PubMed]
  3. Chakkaravarthi, G., Dhayalan, V., Mohanakrishnan, A. K. & Manivannan, V. (2008). Acta Cryst. E64, o542. [DOI] [PMC free article] [PubMed]
  4. Chakkaravarthi, G., Ramesh, N., Mohanakrishnan, A. K. & Manivannan, V. (2007). Acta Cryst. E63, o3564.
  5. Nieto, M. J., Alovero, F. L., Manzo, R. H. & Mazzieri, M. R. (2005). Eur. J. Med. Chem.40, 361–369. [DOI] [PubMed]
  6. Olgen, S. & Coban, T. (2003). Biol. Pharm. Bull.26, 736–738. [DOI] [PubMed]
  7. Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  8. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  9. Spek, A. L. (2003). J. Appl. Cryst.36, 7–13.

Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007678/bt2689sup1.cif

e-64-0o749-sup1.cif (18.4KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808007678/bt2689Isup2.hkl

e-64-0o749-Isup2.hkl (133.2KB, hkl)

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

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography

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