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Acta Crystallographica Section E: Structure Reports Online logoLink to Acta Crystallographica Section E: Structure Reports Online
. 2010 May 19;66(Pt 6):o1376. doi: 10.1107/S1600536810017101

Phen­yl(pyrrolo[2,1-a]isoquinolin-3-yl)methanone

Yun Liu a,*, Hong Jiang b
PMCID: PMC2979433  PMID: 21579457

Abstract

In the title compound, C19H13NO, the fused isoquinoline–pyrrole system is planar (r.m.s. deviation = 0.0249] Å) and makes a dihedral angle of 53.73 (9)° with the phenyl ring. An intra­molecular C—H⋯O inter­action generates an S(6) ring motif.

Related literature

For the biological activity of indolizine, see: Olden et al. (1991 ▶); Jaffrezou et al. (1992 ▶). For our work on the direct one-pot syntheses of pyrrolo[2,1-a]isoquinolines, see: Liu et al. (2010 ▶). For the preparation of pyrrolo[2,1-a]isoquinoline, see: Verna et al. (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶).graphic file with name e-66-o1376-scheme1.jpg

Experimental

Crystal data

  • C19H13NO

  • M r = 271.30

  • Monoclinic, Inline graphic

  • a = 28.637 (6) Å

  • b = 4.0400 (8) Å

  • c = 11.824 (2) Å

  • β = 101.02 (3)°

  • V = 1342.7 (5) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 295 K

  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer

  • Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995 ▶) T min = 0.976, T max = 0.992

  • 2351 measured reflections

  • 2351 independent reflections

  • 1388 reflections with I > 2σ(I)

  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.072

  • wR(F 2) = 0.139

  • S = 1.00

  • 2351 reflections

  • 190 parameters

  • H-atom parameters constrained

  • Δρmax = 0.23 e Å−3

  • Δρmin = −0.30 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810017101/ds2027sup1.cif

e-66-o1376-sup1.cif (18.2KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017101/ds2027Isup2.hkl

e-66-o1376-Isup2.hkl (115.5KB, 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
C19—H19A⋯O 0.93 2.31 2.875 (4) 119
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Acknowledgments

The authors thank Xuzhou Normal University (08XLR07) for financial support. This work was also sponsored by the Qing Lan Project (08QLT001).

supplementary crystallographic information

Comment

The natural and many synthetic indolizines have a diversity of biological activity and are playing an increasingly important role in developing new pharmaceuticals [Olden et al., 1991; Jaffrezou et al., 1992]. Pyrrolo[2,1-a]- isoquinolines are 7,8- benzo- fused indolizines and occur in several marine alkaloids. The synthesis of these structures is drawing much recent research interest [Verna et al., 2009]. In our research work on the direct one pot syntheses of pyrrolo[2,1-a]isoquinolines [Liu et al., 2010], we have prepared the title compound, (I), as one of the products. As part of this study, we have undertaken an X-ray crystallographic analysis of (I) in order to confirm its structure. The bond lengths and angles of the title molecule (Fig. 1) are within normal ranges (Allen et al., 1987). he fused isoquinoline-pyrrole moiety is planar. The dihedral angle between the isoquinoline-pyrrole fused ring and benzene ring is 53.73 (9)°. Although atoms C8, C11 and C19 attached to atom N are all of sp2 hybridization, their different environments cause slight differences in the N—C8, N—C11 and N—C19 bond lengths, and in the C19— N—C11, C19— N—C8 , C11—N—C8 and C10—C11—N angles (Table 1). An intramolecular C—H···O weak hydrogen bond generating an S(6) ring is observed (Table 2). The crystal packing is stabilized by van der Waals forces.

Experimental

The compound (I) was prepared by the reaction of DMF solution of 2-(2-oxo-2- phenylethyl)isoquinolinium bromide with an excess amount of maleic acid in the presence of TPCD and potassium carbonate. After the reaction was completed, the mixture was isolated by chromatography on a silica gel column after evaporation of the solvent. Single crystals of (I) were obtained by slow evaporation from an petroleum ether-ethyl acetate(3:1) solvent system (yield 80%).

Refinement

The H atoms were geometrically placed and were treated as riding, with C—H = 0.93Å .

Figures

Fig. 1.

Fig. 1.

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The molecular structure of (I), with atom labels and 50% probability displacement ellipsoids for non-H atoms.

Crystal data

C19H13NO F(000) = 568
Mr = 271.30 Dx = 1.342 Mg m−3
Monoclinic, P21/c Melting point: 413 K
Hall symbol: -P 2ybc Mo Kα radiation, λ = 0.71073 Å
a = 28.637 (6) Å Cell parameters from 25 reflections
b = 4.0400 (8) Å θ = 9–12°
c = 11.824 (2) Å µ = 0.08 mm−1
β = 101.02 (3)° T = 295 K
V = 1342.7 (5) Å3 Block, colourless
Z = 4 0.30 × 0.20 × 0.10 mm
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Data collection

Enraf–Nonius CAD-4 diffractometer 1388 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube Rint = 0.0000
graphite θmax = 25.0°, θmin = 1.5°
ω/2θ scans h = −34→33
Absorption correction: ψ scan (XCAD4; Harms & Wocadlo, 1995) k = 0→4
Tmin = 0.976, Tmax = 0.992 l = 0→14
2351 measured reflections 3 standard reflections every 200 reflections
2351 independent reflections intensity decay: none
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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)] = 0.072 H-atom parameters constrained
wR(F2) = 0.139 w = 1/[σ2(Fo2) + (0.015P)2 + 2.250P] where P = (Fo2 + 2Fc2)/3
S = 1.00 (Δ/σ)max < 0.001
2351 reflections Δρmax = 0.23 e Å−3
190 parameters Δρmin = −0.29 e Å−3
0 restraints Absolute structure: (XCAD4; Harms & Wocadlo, 1995)
Primary atom site location: structure-invariant direct methods
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Special details

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.
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) 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.
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Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

x y z Uiso*/Ueq
N 0.22455 (9) 0.5534 (7) 0.9319 (2) 0.0382 (7)
C11 0.19331 (11) 0.4146 (9) 0.9955 (3) 0.0402 (9)
C7 0.31218 (12) 0.5686 (10) 0.9370 (3) 0.0485 (10)
O 0.30873 (9) 0.6625 (9) 0.8377 (2) 0.0725 (10)
C12 0.14286 (12) 0.4449 (10) 0.9532 (3) 0.0447 (9)
C3 0.36071 (11) 0.5108 (10) 1.0092 (3) 0.0453 (9)
C8 0.27112 (11) 0.4828 (9) 0.9873 (3) 0.0402 (9)
C19 0.20843 (12) 0.7328 (10) 0.8334 (3) 0.0461 (9)
H19A 0.2302 0.8309 0.7947 0.055*
C18 0.16185 (12) 0.7680 (10) 0.7927 (3) 0.0513 (10)
H18A 0.1517 0.8929 0.7265 0.062*
C2 0.37259 (12) 0.6034 (10) 1.1233 (3) 0.0521 (10)
H2A 0.3496 0.6935 1.1600 0.062*
C17 0.12699 (12) 0.6158 (10) 0.8496 (3) 0.0483 (10)
C9 0.26796 (12) 0.3050 (10) 1.0848 (3) 0.0458 (9)
H9A 0.2936 0.2284 1.1389 0.055*
C10 0.22029 (12) 0.2579 (10) 1.0897 (3) 0.0477 (10)
H10A 0.2086 0.1416 1.1462 0.057*
C13 0.10950 (12) 0.3043 (10) 1.0117 (3) 0.0528 (10)
H13A 0.1197 0.1878 1.0798 0.063*
C14 0.06138 (14) 0.3388 (13) 0.9681 (4) 0.0706 (14)
H14A 0.0393 0.2498 1.0080 0.085*
C16 0.07802 (13) 0.6403 (12) 0.8072 (3) 0.0628 (12)
H16A 0.0672 0.7509 0.7382 0.075*
C6 0.45267 (14) 0.4265 (12) 1.1284 (4) 0.0711 (13)
H6A 0.4837 0.3990 1.1684 0.085*
C15 0.04577 (15) 0.5046 (13) 0.8655 (4) 0.0711 (14)
H15A 0.0134 0.5238 0.8361 0.085*
C4 0.39519 (13) 0.3782 (11) 0.9543 (3) 0.0567 (11)
H4A 0.3875 0.3207 0.8769 0.068*
C5 0.44071 (14) 0.3323 (12) 1.0152 (4) 0.0684 (13)
H5A 0.4635 0.2365 0.9792 0.082*
C1 0.41862 (13) 0.5626 (12) 1.1833 (3) 0.0650 (12)
H1A 0.4267 0.6263 1.2602 0.078*
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Atomic displacement parameters (Å2)

U11 U22 U33 U12 U13 U23
N 0.0359 (15) 0.0496 (19) 0.0307 (13) 0.0024 (15) 0.0101 (11) −0.0003 (15)
C11 0.0396 (19) 0.048 (2) 0.0360 (17) −0.0023 (18) 0.0148 (15) −0.0037 (18)
C7 0.046 (2) 0.064 (3) 0.0387 (18) 0.013 (2) 0.0169 (16) 0.007 (2)
O 0.0555 (17) 0.117 (3) 0.0500 (15) 0.0072 (19) 0.0227 (13) 0.0212 (19)
C12 0.0393 (19) 0.050 (2) 0.047 (2) −0.0018 (19) 0.0148 (16) −0.013 (2)
C3 0.0328 (18) 0.058 (3) 0.049 (2) 0.0002 (19) 0.0162 (16) 0.007 (2)
C8 0.0398 (19) 0.050 (2) 0.0334 (17) 0.0048 (18) 0.0122 (14) 0.0029 (18)
C19 0.051 (2) 0.057 (3) 0.0318 (17) 0.006 (2) 0.0117 (15) 0.0012 (19)
C18 0.049 (2) 0.064 (3) 0.0399 (19) 0.017 (2) 0.0073 (16) 0.009 (2)
C2 0.043 (2) 0.062 (3) 0.054 (2) −0.002 (2) 0.0160 (17) 0.000 (2)
C17 0.0379 (19) 0.061 (3) 0.046 (2) 0.008 (2) 0.0071 (15) −0.010 (2)
C9 0.0394 (19) 0.060 (3) 0.0387 (18) 0.008 (2) 0.0095 (15) 0.0068 (19)
C10 0.045 (2) 0.061 (3) 0.0396 (18) −0.007 (2) 0.0161 (15) 0.006 (2)
C13 0.046 (2) 0.057 (3) 0.059 (2) −0.008 (2) 0.0191 (18) −0.010 (2)
C14 0.041 (2) 0.091 (4) 0.085 (3) −0.015 (3) 0.026 (2) −0.028 (3)
C16 0.046 (2) 0.075 (3) 0.064 (2) 0.012 (2) 0.0013 (19) −0.008 (3)
C6 0.040 (2) 0.082 (4) 0.090 (3) −0.004 (2) 0.008 (2) 0.022 (3)
C15 0.042 (2) 0.083 (4) 0.086 (3) 0.003 (3) 0.007 (2) −0.027 (3)
C4 0.046 (2) 0.064 (3) 0.066 (2) 0.003 (2) 0.0244 (19) −0.002 (2)
C5 0.048 (2) 0.068 (3) 0.097 (3) 0.006 (2) 0.033 (2) 0.005 (3)
C1 0.048 (2) 0.085 (3) 0.060 (2) −0.012 (3) 0.0059 (19) 0.003 (3)
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Geometric parameters (Å, °)

N—C19 1.374 (4) C17—C16 1.399 (5)
N—C11 1.392 (4) C9—C10 1.390 (4)
N—C8 1.399 (4) C9—H9A 0.9300
C11—C10 1.382 (5) C10—H10A 0.9300
C11—C12 1.441 (4) C13—C14 1.383 (5)
C7—O 1.220 (4) C13—H13A 0.9300
C7—C8 1.458 (4) C14—C15 1.383 (6)
C7—C3 1.504 (5) C14—H14A 0.9300
C12—C13 1.402 (5) C16—C15 1.368 (6)
C12—C17 1.404 (5) C16—H16A 0.9300
C3—C2 1.379 (5) C6—C5 1.371 (5)
C3—C4 1.388 (4) C6—C1 1.385 (5)
C8—C9 1.376 (4) C6—H6A 0.9300
C19—C18 1.336 (4) C15—H15A 0.9300
C19—H19A 0.9300 C4—C5 1.376 (5)
C18—C17 1.444 (5) C4—H4A 0.9300
C18—H18A 0.9300 C5—H5A 0.9300
C2—C1 1.382 (5) C1—H1A 0.9300
C2—H2A 0.9300
C19—N—C11 121.6 (3) C8—C9—C10 109.2 (3)
C19—N—C8 129.8 (3) C8—C9—H9A 125.4
C11—N—C8 108.5 (3) C10—C9—H9A 125.4
C10—C11—N 107.6 (3) C11—C10—C9 107.8 (3)
C10—C11—C12 133.4 (3) C11—C10—H10A 126.1
N—C11—C12 118.9 (3) C9—C10—H10A 126.1
O—C7—C8 123.0 (3) C14—C13—C12 120.0 (4)
O—C7—C3 119.4 (3) C14—C13—H13A 120.0
C8—C7—C3 117.4 (3) C12—C13—H13A 120.0
C13—C12—C17 119.5 (3) C13—C14—C15 120.5 (4)
C13—C12—C11 121.8 (3) C13—C14—H14A 119.7
C17—C12—C11 118.7 (3) C15—C14—H14A 119.7
C2—C3—C4 119.8 (3) C15—C16—C17 121.2 (4)
C2—C3—C7 122.8 (3) C15—C16—H16A 119.4
C4—C3—C7 117.2 (3) C17—C16—H16A 119.4
C9—C8—N 106.9 (3) C5—C6—C1 120.1 (4)
C9—C8—C7 130.8 (3) C5—C6—H6A 119.9
N—C8—C7 122.1 (3) C1—C6—H6A 119.9
C18—C19—N 120.8 (3) C16—C15—C14 120.0 (4)
C18—C19—H19A 119.6 C16—C15—H15A 120.0
N—C19—H19A 119.6 C14—C15—H15A 120.0
C19—C18—C17 121.2 (3) C5—C4—C3 119.7 (4)
C19—C18—H18A 119.4 C5—C4—H4A 120.2
C17—C18—H18A 119.4 C3—C4—H4A 120.2
C3—C2—C1 120.2 (4) C6—C5—C4 120.5 (4)
C3—C2—H2A 119.9 C6—C5—H5A 119.7
C1—C2—H2A 119.9 C4—C5—H5A 119.7
C16—C17—C12 118.8 (4) C6—C1—C2 119.6 (4)
C16—C17—C18 122.5 (4) C6—C1—H1A 120.2
C12—C17—C18 118.6 (3) C2—C1—H1A 120.2
C19—N—C11—C10 −178.7 (3) C13—C12—C17—C16 −0.1 (6)
C8—N—C11—C10 −0.2 (4) C11—C12—C17—C16 178.8 (4)
C19—N—C11—C12 3.5 (5) C13—C12—C17—C18 178.0 (4)
C8—N—C11—C12 −178.0 (3) C11—C12—C17—C18 −3.0 (5)
C10—C11—C12—C13 1.4 (7) C19—C18—C17—C16 −178.2 (4)
N—C11—C12—C13 178.5 (3) C19—C18—C17—C12 3.8 (6)
C10—C11—C12—C17 −177.5 (4) N—C8—C9—C10 1.2 (4)
N—C11—C12—C17 −0.4 (5) C7—C8—C9—C10 −173.2 (4)
O—C7—C3—C2 138.8 (4) N—C11—C10—C9 0.9 (4)
C8—C7—C3—C2 −46.0 (6) C12—C11—C10—C9 178.2 (4)
O—C7—C3—C4 −36.8 (6) C8—C9—C10—C11 −1.3 (5)
C8—C7—C3—C4 138.3 (4) C17—C12—C13—C14 −1.0 (6)
C19—N—C8—C9 177.8 (3) C11—C12—C13—C14 −179.9 (4)
C11—N—C8—C9 −0.6 (4) C12—C13—C14—C15 1.6 (7)
C19—N—C8—C7 −7.2 (6) C12—C17—C16—C15 0.7 (6)
C11—N—C8—C7 174.4 (3) C18—C17—C16—C15 −177.3 (4)
O—C7—C8—C9 162.9 (4) C17—C16—C15—C14 −0.2 (7)
C3—C7—C8—C9 −12.1 (6) C13—C14—C15—C16 −1.0 (7)
O—C7—C8—N −10.8 (6) C2—C3—C4—C5 1.7 (6)
C3—C7—C8—N 174.2 (3) C7—C3—C4—C5 177.5 (4)
C11—N—C19—C18 −2.9 (5) C1—C6—C5—C4 1.4 (7)
C8—N—C19—C18 178.9 (4) C3—C4—C5—C6 −2.2 (7)
N—C19—C18—C17 −0.8 (6) C5—C6—C1—C2 −0.1 (7)
C4—C3—C2—C1 −0.4 (6) C3—C2—C1—C6 −0.4 (7)
C7—C3—C2—C1 −175.9 (4)
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Hydrogen-bond geometry (Å, °)

D—H···A D—H H···A D···A D—H···A
C19—H19A···O 0.93 2.31 2.875 (4) 119
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Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DS2027).

References

  1. Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
  2. Enraf–Nonius (1989). CAD-4 Software Enraf–Nonius, Delft, The Netherlands.
  3. Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  4. Jaffrezou, J. P., Levade, T., Thurneyssen, O., Chiron, M., Bordier, C., Attal, M., Chatelain, P. & Laurent, G. (1992). Cancer Res.52, 1352–1359. [PubMed]
  5. Liu, Y., Zhang, Y., Shen, Y.-M., Hu, H.-W. & Xu, J.-H. (2010). Org. Biomol. Chem. doi:10.1039/c000277a.
  6. Olden, K., Breton, P., Grzegorzevski, K., Yasuda, Y., Gause, B. L., Creaipe, O. A., Newton, S. A. & White, S. L. (1991). Pharmacol. Ther.50, 285–290. [DOI] [PubMed]
  7. Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [DOI] [PubMed]
  8. Spek, A. L. (2009). Acta Cryst. D65, 148–155. [DOI] [PMC free article] [PubMed]
  9. Verna, A. K., Kesharwani, T., Singh, J., Tandon, V. & Larock, R. C. (2009). Angew. Chem. Int. Ed.48, 1138–1143. [DOI] [PubMed]

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/S1600536810017101/ds2027sup1.cif

e-66-o1376-sup1.cif (18.2KB, cif)

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017101/ds2027Isup2.hkl

e-66-o1376-Isup2.hkl (115.5KB, 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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