(E) 1 Benzyl 3 (2 nitro­vinyl) 1H indole

organic papers

o3328

17H14N2O2 doi:10.1107/S1600536806026523 Acta Cryst.(2006). E62, o3328–o3330

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

(

E

)-1-Benzyl-3-(2-nitrovinyl)-1

H

-indole

Vijayakumar N. Sonar,aSean Parkinband Peter A. Crooksa*

a

Department of Pharmaceutical Sciences, College of Pharmacy, University of Kentucky, Lexington, KY 40536, USA, andb_{Department of}

Chemistry, University of Kentucky, Lexington, KY 40506, USA

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 150 K

Mean(C–C) = 0.002 A˚ Rfactor = 0.046 wRfactor = 0.125

Data-to-parameter ratio = 16.8

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 28 June 2006 Accepted 7 July 2006

#2006 International Union of Crystallography

All rights reserved

In the title molecule, C17H14N2O2, the indole ring system is

essentially planar and makes a dihedral angle of 87.93 (3)

with the plane of the benzene ring. The nitrovinyl double bond

adopts theEgeometry.

Comment

Tryptamine is an endogenous amine found in the human brain. Serotonin and melatonin are two other essential tryptamines present in the human body. Tryptamine and its analogues can be readily synthesized by reduction of 3-(2-nitrovinyl)indoles (Shen et al., 1998). The title compound is a synthetic inter-mediate in the synthesis of 1-benzyltryptamine, prepared by condensation of 1-benzylindole-3-carboxaldehyde with nitro-methane in the presence of ammonium acetate to afford (E )-1-benzyl-3-(2-nitrovinyl)-1H-indole, (I), as a single geome-trical isomer. The structure of (I) was initially identified by NMR spectroscopy. In order to confirm the double-bond geometry of the nitrovinyl group, its crystal structure deter-mination has been carried out.

The molecular structure and atom-numbering scheme of (I) are shown in Fig. 1. Selected geometric parameters are presented in Table 1. The title compound is theEisomer with the C17—N2 bond in atransdisposition with respect to the C2—C16 bond. The indole ring system is nearly planar [with an r.m.s. deviation of all atoms of 0.009 (1) A˚ ], and makes a dihedral angle of 87.93 (3)with the plane of the benzene ring. The indole ring system is almost coplanar with the plane of the

C16 C17 bond, as is evident from the C1—C2—C16—C17

results in shortening of the bonds C2—C16 and C17—N2, and explains the highly coloured and crystalline nature of the title compound. In the crystal structure, molecules form

centro-symmetric dimers through weak intermolecular C—H O

hydrogen bonds (Fig. 2 and Table 2).

Experimental

The title compound was prepared according to the general procedure reported by Sonar et al. (2005). The compound was obtained as yellow crystals.

Crystal data

C17H14N2O2

Mr= 278.30

Monoclinic,P21=n

a= 4.9846 (1) A˚

b= 16.5617 (5) A˚

c= 16.9822 (6) A˚ = 97.2220 (14)

V= 1390.82 (7) A˚3

Z= 4

Dx= 1.329 Mg m

3

MoKradiation = 0.09 mm1

T= 150.0 (2) K Cut needle, yellow 0.420.240.13 mm

Data collection

Nonius KappaCCD diffractometer !scans

Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)

Tmin= 0.964,Tmax= 0.989

5144 measured reflections 3189 independent reflections 2202 reflections withI> 2(I)

Rint= 0.026

max= 27.5

Refinement

Refinement onF2

R[F2_{> 2(F}2_{)] = 0.046}

wR(F2) = 0.125

S= 1.03 3189 reflections 190 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.0646P)2

+ 0.1702P]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.004

max= 0.20 e A˚

3

min=0.21 e A˚

3

Table 1

Selected geometric parameters (A˚ ,_).

N1—C1 1.3513 (18)

N2—O1 1.2308 (16)

N2—O2 1.2331 (16)

N2—C17 1.4308 (19)

C1—C2 1.386 (2)

C2—C16 1.426 (2)

C16—C17 1.335 (2)

O1—N2—O2 122.61 (13)

O1—N2—C17 120.50 (13)

O2—N2—C17 116.88 (13)

C1—C2—C16 122.82 (14)

N1—C9—C10 111.17 (12)

C17—C16—C2 127.33 (14)

C1—C2—C16—C17 173.60 (14) C2—C16—C17—N2 179.55 (13)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

C1—H1 O1i

0.95 2.46 3.294 (2) 147

Symmetry code: (i)xþ2;yþ1;z.

H atoms were placed in idealized positions and were constrained, with C—H = 0.99 (CH2) and 0.95 A˚ (aromatic and vinyl), andUiso(H)

= 1.2Ueqof the attached C atom.

Data collection: COLLECT (Nonius, 1999); cell refinement:

SCALEPACK (Otwinowski & Minor, 1997); data reduction:

DENZO–SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97(Sheldrick, 1997); program(s) used to refine structure:SHELXL97(Sheldrick, 1997); molecular graphics:

organic papers

Acta Cryst.(2006). E62, o3328–o3330 Sonaret al. _C

17H14N2O2

o3329

Figure 1

The molecular structure of (I), with displacement ellipsoids drawn at the 50% probability level.

Figure 2

XP in SHELXTL (Sheldrick, 1995); software used to prepare material for publication:SHELXL97and local procedures.

This investigation was supported by the National Institute of Alcohol Abuse and Alcoholism Grant AA12600.

References

Nonius (1999).COLLECT. Nonius BV, Delft, The Netherlands.

Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276,

Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.

Sheldrick (1995).XPinSHELXTL/PC. Siemens Analytical Instruments Inc., Madison, Wisconsin, USA.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Shen, G., Chen, G., Cheng, Y., Xie, L. & Miao, L. (1998).Chem. Abstr.130, 13895.

Sonar, V. N., Parkin, S. & Crooks, P. A. (2005).Acta Cryst.C61, o527–o530.

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Acta Cryst. (2006). E62, o3328–o3330

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Acta Cryst. (2006). E62, o3328–o3330 [https://doi.org/10.1107/S1600536806026523]

(

E

)-1-Benzyl-3-(2-nitrovinyl)-1

H

-indole

Vijayakumar N. Sonar, Sean Parkin and Peter A. Crooks

(E)-1-Benzyl-3-(2-nitrovinyl)-1H-indole

Crystal data

C17H14N2O2

Mr = 278.30

Monoclinic, P21/n

Hall symbol: -P 2yn

a = 4.9846 (1) Å

b = 16.5617 (5) Å

c = 16.9822 (6) Å

β = 97.2220 (14)°

V = 1390.82 (7) Å3

Z = 4

F(000) = 584

Dx = 1.329 Mg m−3

Mo Kα radiation, λ = 0.71073 Å

Cell parameters from 3256 reflections

θ = 1.0–27.5°

µ = 0.09 mm−1

T = 150 K

Cut needle, yellow 0.42 × 0.24 × 0.13 mm

Data collection

Nonius KappaCCD diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

Detector resolution: 18 pixels mm-1

ω scans at fixed χ = 55°

Absorption correction: multi-scan

(SCALEPACK; Otwinowski & Minor, 1997)

Tmin = 0.964, Tmax = 0.989

5144 measured reflections 3189 independent reflections 2202 reflections with I > 2σ(I)

Rint = 0.026

θmax = 27.5°, θmin = 1.7°

h = −6→6

k = −21→13

l = −22→22

Refinement

Refinement on F2

Least-squares matrix: full

R[F2 _{> 2σ(F}2_{)] = 0.046}

wR(F2_{) = 0.125}

S = 1.03

3189 reflections 190 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained

w = 1/[σ2_(F

o2) + (0.0646P)2 + 0.1702P] where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.004 Δρmax = 0.20 e Å−3 Δρmin = −0.21 e Å−3

Special details

Experimental. 1_{H NMR (DMSO): δ 5.52 (s, 2H), 7.25–7.34 (m, 7H), 7.62 (d, 1H), 7.99–8.06 (m, 2H), 8.37–8.42 (m, 2H).}

13_{C NMR (DMSO): δ 49.7, 107.7, 111.6, 120.7, 122.1, 123.4, 125.2, 127.1, 127.7, 128.6, 131.4, 133.9, 136.6, 137.3,}

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Acta Cryst. (2006). E62, o3328–o3330

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

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_, conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used}

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

x y z Uiso*/Ueq

N1 1.0120 (2) 0.25929 (7) 0.02568 (7) 0.0260 (3)

N2 0.4717 (3) 0.55589 (8) 0.13336 (7) 0.0340 (3)

O1 0.6092 (2) 0.60541 (7) 0.10216 (7) 0.0456 (3)

O2 0.2786 (3) 0.57562 (7) 0.16796 (8) 0.0547 (4)

C1 0.9789 (3) 0.34027 (9) 0.02556 (8) 0.0279 (3)

H1 1.0688 0.3769 −0.0053 0.033*

C2 0.7961 (3) 0.36264 (8) 0.07664 (8) 0.0268 (3)

C3 0.7099 (3) 0.28814 (9) 0.11085 (8) 0.0250 (3)

C4 0.5359 (3) 0.26817 (9) 0.16659 (9) 0.0297 (3)

H4 0.4386 0.3091 0.1901 0.036*

C5 0.5083 (3) 0.18826 (9) 0.18670 (9) 0.0335 (4)

H5 0.3909 0.1744 0.2245 0.040*

C6 0.6488 (3) 0.12715 (9) 0.15272 (9) 0.0365 (4)

H6 0.6255 0.0726 0.1679 0.044*

C7 0.8216 (3) 0.14474 (9) 0.09726 (9) 0.0322 (4)

H7 0.9170 0.1034 0.0737 0.039*

C8 0.8496 (3) 0.22563 (8) 0.07749 (8) 0.0251 (3)

C9 1.1668 (3) 0.21349 (9) −0.02668 (9) 0.0299 (3)

H9A 1.2831 0.1738 0.0050 0.036*

H9B 1.2855 0.2507 −0.0521 0.036*

C10 0.9814 (3) 0.16970 (9) −0.09025 (8) 0.0254 (3)

C11 0.7668 (3) 0.21082 (10) −0.13243 (8) 0.0313 (4)

H11 0.7384 0.2663 −0.1218 0.038*

C12 0.5940 (3) 0.17109 (11) −0.19001 (9) 0.0369 (4)

H12 0.4460 0.1993 −0.2182 0.044*

C13 0.6355 (3) 0.09083 (11) −0.20676 (9) 0.0360 (4)

H13 0.5168 0.0638 −0.2464 0.043*

C14 0.8503 (3) 0.05007 (9) −0.16564 (9) 0.0359 (4)

H14 0.8806 −0.0050 −0.1773 0.043*

C15 1.0219 (3) 0.08916 (9) −0.10749 (9) 0.0318 (4)

H15 1.1687 0.0606 −0.0791 0.038*

C16 0.7184 (3) 0.44442 (9) 0.08705 (8) 0.0286 (3)

H16 0.8130 0.4842 0.0612 0.034*

C17 0.5276 (3) 0.47137 (9) 0.12908 (8) 0.0306 (4)

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Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

N1 0.0262 (7) 0.0235 (6) 0.0291 (6) −0.0001 (5) 0.0069 (5) −0.0011 (5)

N2 0.0432 (8) 0.0291 (7) 0.0309 (7) 0.0062 (6) 0.0100 (6) 0.0022 (5)

O1 0.0580 (8) 0.0269 (6) 0.0561 (7) 0.0012 (6) 0.0238 (6) 0.0060 (5)

O2 0.0641 (9) 0.0392 (7) 0.0686 (8) 0.0174 (6) 0.0391 (7) 0.0059 (6)

C1 0.0331 (8) 0.0224 (7) 0.0289 (7) −0.0027 (6) 0.0065 (6) 0.0002 (6)

C2 0.0297 (8) 0.0250 (8) 0.0259 (7) −0.0002 (6) 0.0044 (6) −0.0009 (6)

C3 0.0241 (8) 0.0268 (7) 0.0234 (7) −0.0018 (6) 0.0002 (6) −0.0010 (6)

C4 0.0292 (8) 0.0309 (8) 0.0293 (8) −0.0009 (6) 0.0042 (6) 0.0009 (6)

C5 0.0312 (9) 0.0382 (9) 0.0319 (8) −0.0046 (7) 0.0067 (7) 0.0051 (7)

C6 0.0370 (9) 0.0276 (8) 0.0450 (9) −0.0041 (7) 0.0058 (8) 0.0095 (7)

C7 0.0302 (8) 0.0271 (8) 0.0392 (8) 0.0003 (6) 0.0039 (7) 0.0024 (7)

C8 0.0222 (7) 0.0262 (8) 0.0262 (7) −0.0021 (6) 0.0001 (6) 0.0017 (6)

C9 0.0268 (8) 0.0287 (8) 0.0355 (8) 0.0024 (6) 0.0086 (7) −0.0025 (6)

C10 0.0245 (8) 0.0262 (8) 0.0273 (7) 0.0011 (6) 0.0099 (6) 0.0022 (6)

C11 0.0348 (9) 0.0315 (8) 0.0286 (8) 0.0079 (7) 0.0084 (7) 0.0031 (6)

C12 0.0317 (9) 0.0513 (10) 0.0273 (8) 0.0097 (8) 0.0022 (7) 0.0046 (7)

C13 0.0360 (9) 0.0455 (10) 0.0268 (8) −0.0070 (7) 0.0048 (7) −0.0017 (7)

C14 0.0438 (10) 0.0279 (8) 0.0370 (8) −0.0036 (7) 0.0086 (8) −0.0027 (7)

C15 0.0319 (8) 0.0264 (8) 0.0367 (8) 0.0041 (6) 0.0023 (7) 0.0013 (6)

C16 0.0352 (9) 0.0246 (7) 0.0261 (7) −0.0017 (6) 0.0049 (6) 0.0006 (6)

C17 0.0385 (9) 0.0221 (7) 0.0324 (8) 0.0025 (6) 0.0094 (7) 0.0024 (6)

Geometric parameters (Å, º)

N1—C1 1.3513 (18) C7—H7 0.9500

N1—C8 1.3854 (18) C9—C10 1.515 (2)

N1—C9 1.4606 (18) C9—H9A 0.9900

N2—O1 1.2308 (16) C9—H9B 0.9900

N2—O2 1.2331 (16) C10—C15 1.386 (2)

N2—C17 1.4308 (19) C10—C11 1.389 (2)

C1—C2 1.386 (2) C11—C12 1.385 (2)

C1—H1 0.9500 C11—H11 0.9500

C2—C16 1.426 (2) C12—C13 1.380 (2)

C2—C3 1.452 (2) C12—H12 0.9500

C3—C4 1.401 (2) C13—C14 1.379 (2)

C3—C8 1.406 (2) C13—H13 0.9500

C4—C5 1.378 (2) C14—C15 1.383 (2)

C4—H4 0.9500 C14—H14 0.9500

C5—C6 1.396 (2) C15—H15 0.9500

C5—H5 0.9500 C16—C17 1.335 (2)

C6—C7 1.385 (2) C16—H16 0.9500

C6—H6 0.9500 C17—H17 0.9500

C7—C8 1.392 (2)

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C1—N1—C9 126.02 (12) N1—C9—H9A 109.4

C8—N1—C9 124.97 (12) C10—C9—H9A 109.4

O1—N2—O2 122.61 (13) N1—C9—H9B 109.4

O1—N2—C17 120.50 (13) C10—C9—H9B 109.4

O2—N2—C17 116.88 (13) H9A—C9—H9B 108.0

N1—C1—C2 110.74 (13) C15—C10—C11 119.10 (14)

N1—C1—H1 124.6 C15—C10—C9 121.30 (13)

C2—C1—H1 124.6 C11—C10—C9 119.60 (13)

C1—C2—C16 122.82 (14) C12—C11—C10 120.09 (15)

C1—C2—C3 105.93 (12) C12—C11—H11 120.0

C16—C2—C3 131.24 (14) C10—C11—H11 120.0

C4—C3—C8 118.57 (13) C13—C12—C11 120.46 (14)

C4—C3—C2 135.27 (13) C13—C12—H12 119.8

C8—C3—C2 106.15 (12) C11—C12—H12 119.8

C5—C4—C3 118.94 (14) C14—C13—C12 119.59 (14)

C5—C4—H4 120.5 C14—C13—H13 120.2

C3—C4—H4 120.5 C12—C13—H13 120.2

C4—C5—C6 121.51 (15) C13—C14—C15 120.23 (15)

C4—C5—H5 119.2 C13—C14—H14 119.9

C6—C5—H5 119.2 C15—C14—H14 119.9

C7—C6—C5 121.05 (14) C14—C15—C10 120.52 (14)

C7—C6—H6 119.5 C14—C15—H15 119.7

C5—C6—H6 119.5 C10—C15—H15 119.7

C6—C7—C8 117.13 (15) C17—C16—C2 127.33 (14)

C6—C7—H7 121.4 C17—C16—H16 116.3

C8—C7—H7 121.4 C2—C16—H16 116.3

N1—C8—C7 128.65 (14) C16—C17—N2 120.69 (14)

N1—C8—C3 108.55 (12) C16—C17—H17 119.7

C7—C8—C3 122.80 (14) N2—C17—H17 119.7

C8—N1—C1—C2 0.02 (16) C2—C3—C8—N1 −0.10 (15)

C9—N1—C1—C2 173.27 (12) C4—C3—C8—C7 0.2 (2)

N1—C1—C2—C16 −178.66 (13) C2—C3—C8—C7 179.00 (13)

N1—C1—C2—C3 −0.08 (16) C1—N1—C9—C10 −105.27 (16)

C1—C2—C3—C4 178.55 (15) C8—N1—C9—C10 66.91 (17)

C16—C2—C3—C4 −3.0 (3) N1—C9—C10—C15 −132.94 (14)

C1—C2—C3—C8 0.11 (15) N1—C9—C10—C11 47.21 (18)

C16—C2—C3—C8 178.52 (15) C15—C10—C11—C12 1.0 (2)

C8—C3—C4—C5 0.1 (2) C9—C10—C11—C12 −179.20 (13)

C2—C3—C4—C5 −178.24 (15) C10—C11—C12—C13 −0.9 (2)

C3—C4—C5—C6 −0.1 (2) C11—C12—C13—C14 0.1 (2)

C4—C5—C6—C7 −0.1 (2) C12—C13—C14—C15 0.6 (2)

C5—C6—C7—C8 0.4 (2) C13—C14—C15—C10 −0.5 (2)

C1—N1—C8—C7 −178.98 (14) C11—C10—C15—C14 −0.3 (2)

C9—N1—C8—C7 7.7 (2) C9—C10—C15—C14 179.87 (14)

C1—N1—C8—C3 0.05 (15) C1—C2—C16—C17 173.60 (14)

C9—N1—C8—C3 −173.28 (12) C3—C2—C16—C17 −4.6 (3)

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C6—C7—C8—C3 −0.5 (2) O1—N2—C17—C16 −4.2 (2)

C4—C3—C8—N1 −178.85 (11) O2—N2—C17—C16 174.36 (13)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A

C1—H1···O1i _{0.95 2.46 3.294 (2) 147}